JP2005004035A - Method for making planographic printing plate, and planographic printing plate made thereby - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for making a highly sensitive planographic printing plate that is superior in daylight handleability, and excels in printing durability and in shelf life as a planographic printing plate, and to provide a planographic printing plate manufactured by the method. <P>SOLUTION: In the method for making a planographic printing plate, after an image has been exposed on a planographic printing plate material on which a polymerizable compound having an ethylenic unsaturated group on an aluminum support, an optical polymerization initiator, a photosensitive layer containing a sensitizing dye, and an oxygen barrier layer are disposed, in this order; and thereafter heat-treatment is carried out for 5 seconds to 3 minutes at the plate temperature of 80-150°C within 10 minutes, and successively, a development processing is conducted. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

【００５９】
式中、Ｑ^１は
【００６０】
【化２】

【００６１】
又は−Ｓ−を表し、Ｒ^４はアルキル基、ヒドロキシアルキル基又はアリール基を表し、Ｒ^１及びＲ^２は各々、水素原子、アルキル基又はアルコキシアルキル基を表し、Ｒ^３は水素原子、メチル基又はエチル基を表し、Ｘ^１は２〜１２個の炭素原子を有する２価の基を表し、Ｘ^２は、２価の基〜４価の基、又は、
【００６２】
【化３】

【００６３】
を表し、Ｚは、水素原子、アルキル基、アルケニル基、アリール基、ハロゲン原子、アルコキシル基又は複素環基を表し、ｐは１〜４の整数、ｑは１〜３の整数を表す。Ｄ^１及びＤ^２は各々、１〜５個の炭素原子を有する２価の基を表し、Ｅは２〜１２個の炭素原子を有する２価の基、５〜７員環で、且つ窒素原子、酸素原子及び硫黄原子から成る群から選ばれる１種又は２種の原子を含む複素環を有する脂肪族基、６〜１２個の炭素原子を有するアリーレン基、又は５又は６員環を有する芳香族複素環基を表し、ａは０又は１〜４の整数を表し、ｂは０又は１を表し、ｃは１〜３の整数を表し、ｍはＱ^１の原子価により２〜４の整数を表し、ｎは１〜ｍの整数を表し、同一定義の複数の基は互に同一でも異なってもよい。
【００６４】
一般式（１）において、Ｒ^４で表されるアルキル基としては、例えば、メチル、エチル、プロピル、ブチル、ペンチル、ｉ−ペンチル、２−エチルヘキシル、オクチル、デシル、ウンデシル、ドデシル、テトラデシル、ペンタデシル、ヘキサデシル、ヘプタデシル、オクタデシル、ドコサデシル等の各基が挙げられる。
【００６５】
Ｒ^４で表されるヒドロキシアルキル基としては、ヒドロキシメチル、ヒドロキシエチル、ヒドロキシプロピル、ヒドロキシペンチル等の各基が挙げられる。
【００６６】
又、Ｒ^４で表されるアリール基としては、例えば、フェニル、ナフチル等の基が挙げられる。
【００６７】
Ｒ^１及びＲ^２で表されるアルキル基は、上記Ｒ^４で表されるアルキル基と同義である。
【００６８】
Ｒ^１及びＲ^２で表されるアルコキシアルキル基としては、メトキシメチル、メトキシエチル、エトキシメチル、プロポキシエチル等の各基が挙げられる。
【００６９】
Ｘ^１で表される２〜１２個の炭素原子を有する２価の基としては、例えば、飽和炭化水素基、アリーレン基等が挙げられる。又、Ｘ^１で表される２〜１２個の炭素原子を有する飽和炭化水素基としては、エチレン、トリメチレン、テトラメチレン、プロピレン、エチルエチレン、ペンタメチレン、ヘキサメチレン、ヘプタメチレン、オクタメチレン、ノナメチレン、デカメチレン、ウンデカメチレン、ドデカメチレン、シクロヘキシレン（１，６−シクロヘキサンジイル等）、シクロペンチレン（１，５−シクロペンタンジイル等）などが挙げられる。
【００７０】
Ｘ^１で表されるアリーレン基としては、フェニレン、ナフチレン等の基が挙げられる。
【００７１】
Ｘ^２で表される２価の基は、前記Ｘ^１で表される２〜１２個の炭素原子を有する２価の基として挙げられる飽和炭化水素基、アリーレン基等を用いることができるが、更に、前記飽和炭化水素基の中の５個までのメチレン基が酸素原子によって置換されたものを用いることができる。
【００７２】
Ｘ^２で表される３価の基は、上記のＸ^２で表される２価の基（飽和炭化水素基、アリーレン基等）に更に一つ結合基がついたものであり、エタントリイル、プロパントリイル、ブタントリイル、ペンタントリイル、ヘキサントリイル、ヘプタントリイル、オクタントリイル、ノナントリイル、デカントリイル、ウンデカントリイル、ドデカントリイル、シクロヘキサントリイル、シクロペンタントリイル、ベンゼントリイル、ナフタレントリイル等の各基が挙げられる。
【００７３】
又、Ｘ^２で表される４価の基は、上記のＸ^２で表される３価の基に更に一つ結合基がついたものであり、プロパンジイリデン、１，３−プロパンジイル−２−イリデン、ブタンジイリデン、ペンタンジイリデン、ヘキサンジイリデン、ヘプタンジイリデン、オクタンジイリデン、ノナンジイリデン、デカンジイリデン、ウンデカンジイリデン、ドデカンジイリデン、シクロヘキサンジイリデン、シクロペンタンジイリデン、ベンゼンテトライル、ナフタレンテトライル等の各基が挙げられる。
【００７４】
Ｚで表されるアルキル基としては、メチル、エチル、プロピル、ブチル、ペンチル、ｉ−ペンチル、２−エチルヘキシル、オクチル、デシル等の各基が挙げられる。
【００７５】
Ｚで表されるアルケニル基としては、２−プロペニル、３−ブテニル、１−メチル−３−プロペニル、３−ペンテニル、１−メチル−３−ブテニル、４−ヘキセニル等の各基が挙げられる。Ｚで表されるアリール基としては、フェニル、ｍ−クロロフェニル、ｐ−トリル、ナフチル等が挙げられる。
【００７６】
又、Ｚで表されるハロゲン原子としては、弗素、塩素、臭素、沃素等が挙げられる。
【００７７】
Ｚで表されるアルコキシル基としては、メトキシ、エトキシ、プロポキシ、ブトキシ等が挙げられる。
【００７８】
Ｚで表される複素環基としては、ピリジル、ピロリル、２−メチルピロリル、インドリル、イミダゾリル、フリル、チアゾリル、ピリミジニル等の基が挙げられる。
【００７９】
Ｄ^１及びＤ^２で表される１〜５個の炭素原子を有する２価の基としては、メチレン、トリメチレン、テトラメチレン、プロピレン、エチルエチレン、ペンタメチレン、シクロペンチレン等の各基が挙げられる。
【００８０】
Ｅで表される２〜１２個の炭素原子を有する２価の基は、Ｘ^１で表される２〜１２個の炭素原子を有する２価の基と同義である。
【００８１】
Ｅで表される、５〜７員環で、且つ窒素原子、酸素原子及び硫黄原子から成る群から選ばれる１種又は２種の原子を含む複素環を置換基として有する脂肪族基を構成する複素環としては、ピリジン、フラン、ピロール、ピラゾール、イミダゾール、オキサゾール、チアゾール、ピリミジン、ピリダジン、ピラン、チオフェン、イソオキサゾール、ピロリン、イミダゾリン、イミダゾリジン、ピラゾリジン、ピラゾリン、ピペリジン、ピペラジン、モルホリン、キヌクリジン等の各環が挙げられる。
【００８２】
前記の脂肪族基としては、上記記載の複素環を有する炭素数２〜１２の２価の基が挙げられ、前記２価の基は、Ｘ^１で表される２〜１２個の炭素原子を有する２価の基と同義である。
【００８３】
Ｅで表される６〜１２個の炭素原子を有するアリーレン基としては、例えばフェニレン、ナフチレン等の基が挙げられる。
【００８４】
Ｅで表される５又は６員環を有する芳香族複素環基を構成する芳香族複素環としては、フラン、ピロール、ピラゾール、イミダゾール、オキサゾール、チアゾール、１，２，３−オキサジアゾール、１，２，３−トリアゾール、１，２，４−トリアゾール、１，３，４−チアジアゾール、ピリジン、ピリダジン、ピリミジン、ピラジン、ｓ−トリアジン、ベンゾフラン、インドール、ベンゾチオフェン、ベンズイミダゾール、ベンゾチアゾール、プリン、キノリン及びイソキノリン等の各環が挙げられる。
【００８５】
上記一般式（１）で表される各々の置換基は、更に置換基を有してもよい。
又、一般式（１）で表される化合物は、当該業者周知の方法、例えば、米国特許２，５０９，２８８号明細書等に記載の方法を参照して合成できる。
【００８６】
以下、一般式（１）で表される化合物の具体例を挙げるが、本発明はこれらに限定されない。
【００８７】
【化４】

【００８８】
【化５】

【００８９】
【化６】

【００９０】
下記一般式（２）で表されるエチレン性不飽和基を含有する化合物も好ましい。
【００９１】
【化７】

【００９２】
式中、Ｑ^２は
【００９３】
【化８】

【００９４】
を表し、Ｒ^８はアルキル基、ヒドロキシアルキル基又はアリール基を表し、Ｒ^５及びＲ^６は各々、水素原子、アルキル基又はアルコキシアルキル基を表し、Ｒ^７は水素原子、メチル基又はエチル基を表し、Ｄ^３及びＤ^４は各々１〜５個の炭素原子を有する飽和炭化水素基を表し、Ｆは２〜１２個の炭素原子を有する飽和炭化水素基、５〜７員環で、且つ２個までのＮ、Ｏ又はＳ原子を員環として含有する環状脂肪族基、６〜１２個の炭素原子を有するアリーレン基、又は５〜６員環を有する複素環芳香族基を表し、ｄ及びｅは１〜４の整数を表し、ｇはＱ^２の原子価により２〜４の整数を表し、ｆは１〜ｇの整数を表し、同一定義の複数の基は互に同一でも異なってもよい。
【００９５】
上記一般式（２）において、Ｒ^８は（ｇ−ｆ）が２以上の場合は、互いに異なってもよい。ｇとｆが同じ値である化合物が好ましい。Ｒ^８がアルキル基、ヒドロキシアルキル基の場合は、炭素数２〜８が好ましく、２〜４がより好ましい。Ｒ^８がアリール基の場合は、単環または２環が好ましく、単環がより好ましく、且つ炭素数５個までのアルキル基、アルコキシアルキル基又はハロゲン原子で置換されてもよい。
【００９６】
Ｒ^５及びＲ^６がアルキル基又はアルコキシアルキル基の場合は、炭素数１〜５が好ましい。Ｒ^７はメチル基が好ましい。
【００９７】
Ｄ^３及びＤ^４は同一でも異なってもよく、且つ２個の窒素原子を含む６員の飽和複素環が好ましい。
【００９８】
Ｆが飽和炭化水素基の場合は２〜６個の炭素原子を有することが好ましく、Ｆがアリーレン基の場合はフェニレン基が好ましく、環状脂肪族基の場合はシクロヘキシレン基が好ましく、複素環芳香族基の場合は窒素原子又は硫黄原子を含む５〜６員環が好ましい。
【００９９】
一般式（２）で表される化合物を得るには、Ｑ^２がＮであり、ｇとｆが同じ値の場合は、グリシジルアクリレート又はアルキルアクリレートをヒドロキシアルキルアミンと反応させる。他の化合物も同様にして得ることができる。
【０１００】
一般式（２）で表される化合物の具体例を以下に示す。
【０１０１】
【化９】

【０１０２】
本発明に係る平版印刷版材料の感光層には、上記したエチレン性不飽和基を含有する重合可能な化合物を総量として５〜９９質量％の範囲で含有することが好ましく、１０〜９８質量％の範囲がより好ましく、２０〜９７質量％の範囲が特に好ましい。
【０１０３】
（光重合開始剤）
光重合開始剤はエチレン性不飽和基を含有する重合可能な化合物の重合を開始させる化合物であり、チタノセン化合物、金属アレーン化合物、モノアルキルトリアリールボレート化合物が挙げられる。この中でも、金属アレーン化合物が好ましく、下記構造式で示される。
【０１０４】
【化１０】

【０１０５】
式中、Ｍは鉄、ニッケル、コバルト等の金属原子、Ｘ⁻はＢＦ^４−、ＰＦ^６−、ＡｓＦ^６−、ＳｂＦ^６−等の塩基性イオン、Ｙはベンゼン環を少なくとも一つは含む基を表す。
【０１０６】
金属アレーン化合物として望ましいのは、鉄アレーン化合物、クロムアレーン化合物、マンガンアレーン化合物、コバルトアレーン化合物、ニッケルアレーン化合物等であるが、中でも、鉄アレーン化合物を用いるとより一層の感度向上を図ることができ好ましい。
【０１０７】
鉄アレーン化合物としては、例えば、特開昭５９−２１９３０７号公報に記載の化合物が挙げられるが、更に好ましい具体例として、η−ベンゼン−（η−シクロペンタジエニル）鉄・ヘキサフルオロホスフェート、η−クメン−（η−シクロペンタジエニル）鉄・ヘキサフルオロホスフェート、η−フルオレン−（η−シクロペンタジエニル）鉄・ヘキサフルオロホスフェート、η−ナフタレン−（η−シクロペンタジエニル）鉄・ヘキサフルオロホスフェート、η−キシレン−（η−シクロペンタジエニル）鉄・ヘキサフルオロホスフェート、η−ベンゼン−（η−シクロペンタジエニル）鉄・テトラフルオロボレート等が挙げられる。
【０１０８】
チタノセン化合物としては、特開昭６３−４１４８３号公報、特開平２−２９１号公報に記載される化合物等が挙げられるが、更に好ましい具体例としては、ビス（シクロペンタジエニル）−Ｔｉ−ジ−クロライド、ビス（シクロペンタジエニル）−Ｔｉ−ビス−フェニル、ビス（シクロペンタジエニル）−Ｔｉ−ビス−２，３，４，５，６−ペンタフルオロフェニル、ビス（シクロペンタジエニル）−Ｔｉ−ビス−２，３，５，６−テトラフルオロフェニル、ビス（シクロペンタジエニル）−Ｔｉ−ビス−２，４，６−トリフルオロフェニル、ビス（シクロペンタジエニル）−Ｔｉ−ビス−２，６−ジフルオロフェニル、ビス（シクロペンタジエニル）−Ｔｉ−ビス−２，４−ジフルオロフェニル、ビス（メチルシクロペンタジエニル）−Ｔｉ−ビス−２，３，４，５，６−ペンタフルオロフェニル、ビス（メチルシクロペンタジエニル）−Ｔｉ−ビス−２，３，５，６−テトラフルオロフェニル、ビス（メチルシクロペンタジエニル）−Ｔｉ−ビス−２，６−ジフルオロフェニル（ＩＲＵＧＡＣＵＲＥ７２７Ｌ：チバスペシャリティケミカルズ社製）、ビス（シクロペンタジエニル）−ビス（２，６−ジフルオロ−３−（ピリ−１−イル）フェニル）チタニウム（ＩＲＵＧＡＣＵＲＥ７８４：チバスペシャリティケミカルズ社製）、ビス（シクロペンタジエニル）−ビス（２，４，６−トリフルオロ−３−（ピリ−１−イル）フェニル）チタニウムビス（シクロペンタジエニル）−ビス（２，４，６−トリフルオロ−３−（２−５−ジメチルピリ−１−イル）フェニル）チタニウム等が挙げられる。
【０１０９】
又、モノアルキルトリアリールボレート化合物としては、特開昭６２−１５０２４２号公報、同６２−１４３０４４号公報に記載の化合物等挙げられるが、更に好ましい具体例としては、テトラブチルアンモニウム・ブチル−トリナフタレン−１−イル−ボレート、テトラブチルアンモニウム・ブチル−トリフェニルボレート、テトラブチルアンモニウム・ブチル−トリ（４−ｔ−ブチルフェニル）ボレート、テトラブチルアンモニウム・ヘキシル−トリ（３−クロロ−４−メチルフェニル）ボレート、テトラブチルアンモニウム・ヘキシル−トリ（３−フルオロフェニル）ボレート等が挙げられる。
【０１１０】
更に、Ｊ．コーサー（Ｊ．Ｋｏｓａｒ）著「ライト・センシテイブ・システムズ」第５章に記載されるようなカルボニル化合物、有機硫黄化合物、過硫化物、レドックス系化合物、アゾ並びにジアゾ化合物、光還元性色素などが挙げられる。更に具体的な化合物は英国特許第１，４５９，５６３号明細書に開示される。即ち、併用が可能な光重合開始剤としては、以下のようなものを使用することができる。
【０１１１】
ベンゾインメチルエーテル、ベンゾイン−ｉ−プロピルエーテル、α，α−ジメトキシ−α−フェニルアセトフェノン等のベンゾイン誘導体；ベンゾフェノン、２，４−ジクロロベンゾフェノン、ｏ−ベンゾイル安息香酸メチル、４，４′−ビス（ジメチルアミノ）ベンゾフェノン等のベンゾフェノン誘導体；２−クロロチオキサントン、２−ｉ−プロピルチオキサントン等のチオキサントン誘導体；２−クロロアントラキノン、２−メチルアントラキノン等のアントラキノン誘導体；Ｎ−メチルアクリドン、Ｎ−ブチルアクリドン等のアクリドン誘導体；α，α−ジエトキシアセトフェノン、ベンジル、フルオレノン、キサントン、ウラニル化合物の他、特公昭５９−１２８１号公報、同６１−９６２１号公報ならびに特開昭６０−６０１０４号公報記載のトリアジン誘導体；特開昭５９−１５０４号公報、同６１−２４３８０７号公報記載の有機過酸化物；特公昭４３−２３６８４号公報、同４４−６４１３号公報、同４４−６４１３号公報、同４７−１６０４号公報ならびに米国特許３，５６７，４５３号明細書記載のジアゾニウム化合物；米国特許２，８４８，３２８号明細書、同２，８５２，３７９号明細書ならびに同２，９４０，８５３号明細書記載の有機アジド化合物；特公昭３６−２２０６２ｂ号公報、同３７−１３１０９号公報、同３８−１８０１５号公報ならびに同４５−９６１０号公報記載のｏ−キノンジアジド類；特公昭５５−３９１６２号公報、特開昭５９−１４０２３号公報ならびに「マクロモレキュルス（Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ）」１０巻、１３０７頁（１９７７年）記載の各種オニウム化合物；特開昭５９−１４２２０５号公報記載のアゾ化合物；特開平１−５４４４０号公報、欧州特許第１０９，８５１号明細書、同１２６，７１２号明細書ならびに「ジャーナル・オブ・イメージング・サイエンス（Ｊ．Ｉｍａｇ．Ｓｃｉ．）」３０巻、１７４頁（１９８６年）記載の金属アレーン錯体；特開平５−２１３８６１号公報及び同５−２５５３４７号公報記載の（オキソ）スルホニウム有機硼素錯体；「コーディネーション・ケミストリー・レビュー（Ｃｏｏｒｄｉｎａｔｉｏｎ Ｃｈｅｍｉｓｔｒｙ Ｒｅｖｉｅｗ）」８４巻、８５〜２７７頁（１９８８年）ならびに特開平２−１８２７０１号公報記載のルテニウム等の遷移金属を含有する遷移金属錯体；特開平３−２０９４７７号公報記載の２，４，５−トリアリールイミダゾール二量体；四臭化炭素、特開昭５９−１０７３４４号公報記載の有機ハロゲン化合物等。
【０１１２】
（増感色素）
光源にレーザー光を用いる場合、好ましくは感光層に増感色素を添加する。光源の波長付近に吸収極大波長を有する色素を用いることが好ましい。
【０１１３】
可視光から近赤外まで波長増感させる化合物としては、例えば、シアニン、フタロシアニン、メロシアニン、オキソノール、ポルフィリン、スピロ化合物、フェロセン、フルオレン、フルギド、イミダゾール、ペリレン、フェナジン、フェノチアジン、ポリエン、アゾ化合物、ジフェニルメタン、トリフェニルメタン、ポリメチンアクリジン、クマリン、クマリン誘導体、ケトクマリン、キナクリドン、インジゴ、スチリル、ピリリウム化合物、ピロメテン化合物、ピラゾロトリアゾール化合物、ベンゾチアゾール化合物、バルビツール酸誘導体、チオバルビツール酸誘導体等、ケトアルコールボレート錯体が挙げられ、更に欧州特許第５６８，９９３号明細書、米国特許第４，５０８，８１１号明細書、同５，２２７，２２７号明細書、特開２００１−１２５２５５号公報、特開平１１−２７１９６９号公報等に記載の化合物も用いられる。中でも好ましいのは、クマリン、ケトクマリン、オキソノール、バルビツール酸、ピロメテンボレート、ジフェニルメタン骨格を有する色素類である。
【０１１４】
光重合開始剤と増感色素の配合比率は、モル比で１：１００〜１００：１の範囲が好ましい。
【０１１５】
更に、本発明において、画像露光は４５０ｎｍ以下のレーザー光が好ましく、光源のレーザー光として、３９０〜４３０ｎｍの範囲に発光波長を有する半導体レーザー、所謂バイオレットレーザーを用いた記録を行う場合は、３９０〜４３０ｎｍの間に吸収極大有する色素を含有させることが望ましい。３９０〜４３０ｎｍの間に吸収極大有する色素としては構造上特に制約は無いが、上記色素の極大吸収が、この要件を満たす限り、何れも使用可能である。具体的には、特開２００２−２９６７６４号公報、同２００２−２６８２３９号公報、同２００２−２６８２３８号公報、同２００２−２６８２０４号公報、同２００２−２２１７９０号公報、同２００２−２０２５９８号公報、同２００１−４２５２４号公報、同２０００−３０９７２４号公報、同２０００−２５８９１０号公報、同２０００−２０６６９０号公報、同２０００−１４７７６３号公報、同２０００−９８６０５号公報等に記載される色素を用いることができるが、これらに限定されない。
【０１１６】
（バインダー）
本発明に係る平版印刷版材料の感光層用バインダーとしては、上記エチレン性不飽和基を有する重合可能な化合物として記載した、エチレン性不飽和結合を有し、重量平均分子量が１５，０００〜２００，０００、酸価が３０〜２００ｍｇ／ＫＯＨである化合物を好ましく用いることができるが、これらと併せて又は単独で、エチレン性不飽和結合を有しない公知の高分子結合剤を用いることもできる。
【０１１７】
本発明に係る平版印刷版材料は、陽極酸化処理して特定の表面粗さを有する金属支持上に、感光性組成物を含有する感光層と酸素遮断層とをこの順に塗設したものである。
【０１１８】
（支持体）
本発明に用いる支持体は親水性表面を有する、例えば、アルミニウム、ステンレス、クロム、ニッケル等の金属板、又、ポリエステルフィルム、ポリエチレンフィルム、ポリプロピレンフィルム等のプラスチックフィルムに前述の金属薄膜をラミネート又は蒸着したもの等が使用でき、又ポリエステルフィルム、塩化ビニルフィルム、ナイロンフィルム等の表面に親水化処理を施したもの等が使用できるが、アルミニウム支持体が好ましく使用され、この場合、純アルミニウム又はアルミニウム合金であっても構わない。
【０１１９】
支持体のアルミニウム合金としては種々のものが使用でき、例えば、珪素、銅、マンガン、マグネシウム、クロム、亜鉛、鉛、ビスマス、ニッケル、チタン、ナトリウム、鉄等の金属とアルミニウムの合金が用いられる。
【０１２０】
支持体は、粗面化（砂目立て処理）するに先立って表面の圧延油を除去するために脱脂処理を施すことが好ましい。脱脂処理としては、トリクレン、シンナー等の溶剤を用いる脱脂処理、ケロシン、トリエタノール等のエマルジョンを用いたエマルジョン脱脂処理等が用いられる。又、脱脂処理には、水酸化ナトリウム等のアルカリ水溶液を用いることもできる。脱脂処理にアルカリ水溶液を用いた場合、前記脱脂処理のみでは除去できない汚れや酸化皮膜も除去することができる。脱脂処理に水酸化ナトリウム等のアルカリ水溶液を用いた場合、支持体の表面にはスマットが生成するので、この場合には、燐酸、硝酸、硫酸、クロム酸等の酸、あるいは、それらの混酸に浸漬しデスマット処理を施すことが好ましい。
【０１２１】
粗面化の方法としては、例えば、機械的方法、電解によりエッチングする方法が挙げられる。
【０１２２】
機械的粗面化法は特に限定されるものではないが、ブラシ研磨法、ホーニング研磨法が好ましい。ブラシ研磨法による粗面化は、例えば、直径０．２〜０．８ｍｍのブラシ毛を使用した回転ブラシを回転し、支持体表面に、例えば、粒径１０〜１００μｍの火山灰の粒子を水に均一に分散させたスラリーを供給しながら、ブラシを押し付けて行うことができる。ホーニング研磨による粗面化は、例えば、粒径１０〜１００μｍの火山灰の粒子を水に均一に分散させ、ノズルより圧力を掛けて射出し、支持体表面に斜めから衝突させて粗面化を行うことができる。又、例えば、支持体表面に粒径１０〜１００μｍの研磨剤粒子を１００〜２００μｍの間隔で、２．５×１０^３〜１０×１０^３個／ｃｍ^２の密度で存在するように塗布したシートを貼り合わせ、圧力を掛けてシートの粗面パターンを転写することにより粗面化を行うこともできる。
【０１２３】
上記の機械的粗面化法で粗面化した後、支持体の表面に食い込んだ研磨剤、形成されたアルミニウム屑等を取り除くため、酸又はアルカリの水溶液に浸漬することが好ましい。酸としては、例えば、硫酸、過硫酸、弗酸、燐酸、硝酸、塩酸等が用いられ、塩基としては、例えば、水酸化ナトリウム、水酸化カリウム等が用いられる。これらの中でも、水酸化ナトリウム等のアルカリ水溶液を用いるのが好ましい。表面のアルミニウムの溶解量としては、０．５〜５ｇ／ｍ^２が好ましい。
【０１２４】
アルカリ水溶液で浸漬処理を行った後、燐酸、硝酸、硫酸、クロム酸等の酸あるいは、それらの混酸に浸漬し中和処理を施すことが好ましい。
【０１２５】
電気化学的粗面化法も特に限定されるものではないが、酸性電解液中で電気化学的に粗面化を行う方法が好ましい。酸性電解液は、電気化学的粗面化法に通常用いられる酸性電解液を使用することができるが、塩酸系又は硝酸系電解液を用いるのが好ましい。電気化学的粗面化方法については、例えば特公昭４８−２８１２３号公報、英国特許８９６，５６３号明細書、特開昭５３−６７５０７号公報に記載される方法を用いることができる。
【０１２６】
この粗面化法は、一般には、１〜５０Ｖの範囲の電圧を印加することによって行うことができるが、１０〜３０Ｖの範囲から選ぶのが好ましい。電流密度は１０〜２００Ａ／ｄｍ^２の範囲を用いることができるが、５０〜１５０Ａ／ｄｍ^２の範囲から選ぶのが好ましい。電気量は１００〜５０００ｃ／ｄｍ^２の範囲を用いることができるが、１００〜２０００ｃ／ｄｍ^２の範囲から選ぶのが好ましい。粗面化法を行う温度は１０〜５０℃の範囲を用いることができるが、１５〜４５℃の範囲から選ぶのが好ましい。
【０１２７】
電解液として硝酸系電解液を用いて電気化学的粗面化を行う場合、一般には、１〜５０Ｖの範囲の電圧を印加することによって行うことができるが、１０〜３０Ｖの範囲から選ぶのが好ましい。電流密度は１０〜２００Ａ／ｄｍ^２の範囲を用いることができるが、２０〜１００Ａ／ｄｍ^２の範囲から選ぶのが好ましい。電気量は１００〜５０００ｃ／ｄｍ^２の範囲を用いることができるが、１００〜２０００ｃ／ｄｍ^２の範囲から選ぶのが好ましい。電気化学的粗面化法を行う温度は１０〜５０℃の範囲を用いることができるが、１５〜４５℃の範囲から選ぶのが好ましい。電解液における硝酸濃度は０．１〜５質量％が好ましい。電解液には、必要に応じて、硝酸塩、塩化物、アミン類、アルデヒド類、燐酸、クロム酸、硼酸、酢酸、蓚酸等を加えることができる。
【０１２８】
電解液として塩酸系電解液を用いる場合、一般には、１〜５０Ｖの範囲の電圧を印加することによって行うことができるが、２〜３０Ｖの範囲から選ぶのが好ましい。電流密度は、１０〜２００Ａ／ｄｍ^２の範囲を用いることができるが、５０〜１５０Ａ／ｄｍ^２の範囲から選ぶのが好ましい。電気量は１００〜５０００ｃ／ｄｍ^２の範囲を用いることができるが、１００〜２０００ｃ／ｄｍ^２、更には２００〜１０００ｃ／ｄｍ^２の範囲から選ぶのが好ましい。電気化学的粗面化法を行う温度は１０〜５０℃の範囲を用いることができるが、１５〜４５℃の範囲から選ぶのが好ましい。電解液における塩酸濃度は０．１〜５質量％が好ましい。
【０１２９】
上記の電気化学的粗面化法で粗面化した後、表面のアルミニウム屑等を取り除くため、酸又はアルカリの水溶液に浸漬することが好ましい。酸としては、例えば、硫酸、過硫酸、弗酸、燐酸、硝酸、塩酸等が用いられ、塩基としては、例えば、水酸化ナトリウム、水酸化カリウム等が用いられる。これらの中でもアルカリの水溶液を用いるのが好ましい。表面のアルミニウムの溶解量としては、０．５〜５ｇ／ｍ^２が好ましい。又、アルカリの水溶液で浸漬処理を行った後、燐酸、硝酸、硫酸、クロム酸等の酸あるいは、それらの混酸に浸漬し中和処理を施すことが好ましい。
【０１３０】
機械的粗面化処理法、電気化学的粗面化法はそれぞれ単独で用いて粗面化してもよいし、又、機械的粗面化処理法に次いで電気化学的粗面化法を行って粗面化してもよい。
【０１３１】
粗面化処理の次には、陽極酸化処理を行うことができる。本発明において用いることができる陽極酸化処理の方法には特に制限はなく、公知の方法を用いることができる。陽極酸化処理を行うことにより、支持体上には酸化皮膜が形成される。該陽極酸化処理には、硫酸及び／又は燐酸等を１０〜５０％の濃度で含む水溶液を電解液として、電流密度１〜１０Ａ／ｄｍ^２で電解する方法が好ましく用いられるが、他に米国特許第１，４１２，７６８号明細書に記載される硫酸中で高電流密度で電解する方法や、同３，５１１，６６１号明細書に記載される燐酸を用いて電解する方法、クロム酸、蓚酸、マロン酸等を１種又は２種以上含む溶液を用いる方法等が挙げられる。形成された陽極酸化被覆量は１〜５０ｍｇ／ｄｍ^２が適当であり、好ましくは１０〜４０ｍｇ／ｄｍ^２である。陽極酸化被覆量は、例えば、アルミニウム板を燐酸クロム酸溶液（燐酸８５％液：３５ｍｌ、酸化クロム（ＩＶ）：２０ｇを１Ｌの水に溶解して作製）に浸積し、酸化被膜を溶解し、板の被覆溶解前後の質量変化測定等から求められる。
【０１３２】
陽極酸化処理された支持体は、必要に応じ封孔処理を施してもよい。これら封孔処理は、熱水処理、沸騰水処理、水蒸気処理、珪酸ナトリウム処理、重クロム酸塩水溶液処理、亜硝酸塩処理、酢酸アンモニウム処理、リン酸塩処理、ポリビニルホスホン酸（ＰＶＰＡ）処理等公知の方法を用いて行うことができる。
【０１３３】
処理後の支持体表面の中心線平均粗さＲａは０．２〜０．７μｍであることが好ましく、更に０．５〜０．７μｍであることが好ましい。
【０１３４】
更に、これらの処理を行った後に、水溶性の樹脂、例えば、ポリビニルホスホン酸（ＰＶＰＡ）、スルホ基を側鎖に有する重合体及び共重合体、ポリアクリル酸、水溶性金属塩（硼酸亜鉛等）もしくは黄色染料、アミン塩等を下塗りしたものも好適である。更に、特開平５−３０４３５８号公報に開示されているようなラジカルによって付加反応を起し得る官能基を共有結合させたゾル−ゲル処理基板も好適に用いられる。
【０１３５】
（塗布）
調製された感光性組成物（感光層塗布液）は、従来公知の方法で支持体上に塗布・乾燥し、平版印刷版材料を作製することができる。塗布液の塗布方法としては、例えば、エアドクタコータ法、ブレードコータ法、ワイヤバー法、ナイフコータ法、ディップコータ法、リバースロールコータ法、グラビヤコータ法、キャストコーティング法、カーテンコータ法及び押出しコータ法等が挙げられる。
【０１３６】
感光層の乾燥温度は、低いと十分な耐刷性を得ることができず、又高過ぎるとマランゴニーを生じてしまうばかりか、非画線部のカブリを生じてしまう。好ましい乾燥温度範囲としては６０〜１６０℃が好ましく、より好ましくは８０〜１４０℃、特に好ましくは９０〜１２０℃の範囲である。
【０１３７】
（保護層：酸素遮断層）
感光層の上側には保護層を設けることが好ましい。該保護層（酸素遮断層）は、後述の現像液（一般にはアルカリ水溶液）への溶解性が高いことが好ましく、具体的にはポリビニルアルコール及びポリビニルピロリドンを挙げることができる。ポリビニルアルコールは酸素の透過を抑制する効果を有し、又ポリビニルピロリドンは隣接する感光層との接着性を確保する効果を有する。
【０１３８】
上記２種のポリマーの他に、必要に応じてポリサッカライド、ポリエチレングリコール、ゼラチン、膠、カゼイン、ヒドロキシエチルセルロース、カルボキシメチルセルロース、メチルセルロース、ヒドロキシエチル澱粉、アラビアゴム、サクローズオクタアセテート、アルギン酸アンモニウム、アルギン酸ナトリウム、ポリビニルアミン、ポリエチレンオキシド、ポリスチレンスルホン酸、ポリアクリル酸、水溶性ポリアミド等の水溶性ポリマーを併用することもできる。
【０１３９】
本発明に係る平版印刷版材料では、感光層と保護層間の剥離力が３５ｍＮ／ｍｍ以上であることが好ましく、より好ましくは５０ｍＮ／ｍｍ以上、更に好ましくは７５ｍＮ／ｍｍ以上である。好ましい保護層の組成としては特開平１０−１０７４２号公報に記載されるものが挙げられる。剥離力は、保護層上に十分大きい粘着力を有する所定幅の粘着テープを貼り、それを平版印刷版材料の平面に対して９０度の角度で保護層と共に剥離する時の力を測定することにより求められる。
【０１４０】
保護層には、更に必要に応じて界面活性剤、マット剤等を含有することができる。上記保護層組成物を適当な溶剤に溶解し感光層上に塗布・乾燥して保護層を形成する。塗布溶剤の主成分は水、あるいはメタノール、エタノール、ｉ−プロパノール等のアルコール類であることが特に好ましい。保護層の厚みは０．１〜５．０μｍが好ましく、特に好ましくは０．５〜３．０μｍである。
【０１４１】
（画像形成方法）
平版印刷版材料に画像露光する光源としては、例えば、レーザー、発光ダイオード、キセノンランプ、キセノンフラッシュランプ、ハロゲンランプ、カーボンアーク燈、メタルハライドランプ、タングステンランプ、高圧水銀ランプ、無電極光源等を挙げることができる。
【０１４２】
一括露光する場合には、光重合性感光層上に、所望の露光画像のネガパターンを遮光性材料で形成したマスク材料を重ね合わせ、露光すればよい。
【０１４３】
発光ダイオードアレイ等のアレイ型光源を使用する場合や、ハロゲンランプ、メタルハライドランプ、タングステンランプ等の光源を、液晶、ＰＬＺＴ等の光学的シャッター材料で露光制御する場合には、画像信号に応じたデジタル露光をすることが可能であり好ましい。この場合は、マスク材料を使用せず、直接書込みを行うことができる。
【０１４４】
レーザー露光の場合には、光をビーム状に絞り画像データに応じた走査露光が可能なので、マスク材料を使用せず、直接書込みを行うのに適している。又、レーザーを光源として用いる場合には、露光面積を微小サイズに絞ることが容易であり、高解像度の画像形成が可能となる。
【０１４５】
レーザー光源としては、アルゴンレーザー、Ｈｅ−Ｎｅガスレーザー、ＹＡＧレーザー、半導体レーザー等を何れも好適に用いることが可能であるが、本発明においては、ＩｎＧａＮ系やＺｎＳｅ系の材料を用い、３９０〜４３０ｎｍ域で連続発振可能な半導体レーザーを用いることが、本発明の効果を遺憾なく発揮する上で特に好ましい。
【０１４６】
レーザーの走査方法としては、円筒外面走査、円筒内面走査、平面走査などがある。円筒外面走査では、記録材料を外面に巻き付けたドラムを回転させながらレーザー露光を行い、ドラムの回転を主走査としレーザー光の移動を副走査とする。円筒内面走査では、ドラムの内面に記録材料を固定し、レーザービームを内側から照射し、光学系の一部又は全部を回転させることにより円周方向に主走査を行い、光学系の一部又は全部をドラムの軸に平行に直線移動させることにより軸方向に副走査を行う。平面走査では、ポリゴンミラーやガルバノミラーとｆθレンズ等を組み合わせてレーザー光の主走査を行い、記録媒体の移動により副走査を行う。円筒外面走査及び円筒内面走査の方が光学系の精度を高め易く、高密度記録には適している。
【０１４７】
（現像処理）
画像露光した感光層は露光部が硬化する。これをアルカリ現像液で現像処理することにより、未露光部が除去され画像形成が可能となる。この様な現像液としては、従来より知られているアルカリ水溶液が使用できる。例えば、珪酸ナトリウム、同カリウム、同アンモニウム；第二燐酸ナトリウム、同カリウム、同アンモニウム；重炭酸ナトリウム、同カリウム、同アンモニウム；炭酸ナトリウム、同カリウム、同アンモニウム；炭酸水素ナトリウム、同カリウム、同アンモニウム；ホウ酸ナトリウム、同カリウム、同アンモニウム；水酸化ナトリウム、同カリウム、同アンモニウム及び同リチウム等の無機アルカリ剤を使用するアルカリ現像液が挙げられる。
【０１４８】
又、モノメチルアミン、ジメチルアミン、トリメチルアミン、モノエチルアミン、ジエチルアミン、トリエチルアミン、モノ−ｉ−プロピルアミン、ジ−ｉ−プロピルアミン、トリ−ｉ−プロピルアミン、ブチルアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、モノ−ｉ−プロパノールアミン、ジ−ｉ−プロパノールアミン、エチレンイミン、エチレンジアミン、ピリジン等の有機アルカリ剤も用いることができる。
【０１４９】
これらのアルカリ剤は、単独又は２種以上を組み合わせて用いられる。又、該現像液には、必要に応じてアニオン性界面活性剤、両性活性剤やアルコール等の有機溶媒を加えることができる。
【０１５０】
本発明の現像液のｐＨは８．５より高く１３．０未満の範囲であるアルカリ性水溶液であることが好ましく、更に好ましくはｐＨ１０．０〜１２．５である。
【０１５１】
又、使用される現像液の導電率は３〜３０ｍＳ／ｃｍであることが好ましい。この範囲を下回ると、通常、アルミニウム板支持体表面の感光性組成物の溶出が困難となり、印刷での汚れを伴ってしまい、逆に、この範囲を超えると塩濃度が高いため感光層の溶出速度が極端に遅くなり、未露光部に残膜が生じる。導電率の範囲は、更に好ましくは５〜２０ｍＳ／ｃｍである。
【０１５２】
現像液及び補充液には、現像性の促進や現像カスの分散並びに印刷版画像部の親インキ性を高める目的で種々の界面活性剤を添加できる。
【０１５３】
好ましい界面活性剤としては、アニオン系、カチオン系、ノニオン系及び両性界面活性剤が挙げられるが、本発明の現像液は、特にポリオキシアルキレンエーテル基を有するノニオン系界面活性剤またはアニオン系界面活性剤を含有することが好ましい。この型の界面活性剤としては、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアリールエーテル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレンナフチルエーテル、ポリオキシエチレンポリスチリルフェニルエーテル、ポリオキシエチレンポリオキシプロピレンアルキルエーテル等、多くのものが知られている。
【０１５４】
【実施例】
以下、実施例により本発明を更に具体的に説明するが、本発明はこれに限定されるものではない。尚、実施例における「部」は、特に断りない限り「質量部」を表す。
【０１５５】
実施例１
〔本発明１〜８、比較１〜６平版印刷版の作製〕
（バインダーの合成）
窒素気流下の三ツ口フラスコに、メタクリル酸メチル４６．０部（０．４６モル）、メタクリル酸４１．４部（０．４８モル）、メタクリル酸エチル６．７部（０．０６モル）、エタノール１００部及びα，α′−アゾビスイソブチロニトリル１．２３部を入れ、窒素気流中８０℃のオイルバスで６時間反応させて高分子重合体を得た。その後、該重合体にトリエチルベンジルアンモニウムクロライド１部及びグリシジルメタクリレート４２．５部（０．２８モル）を加えて、温度２５℃で３時間反応させて下記構造の高分子結合剤Ａを得た。ＧＰＣを用いて測定した重量平均分子量は約７０，０００であった。
【０１５６】
【化１１】

【０１５７】
以下、表１に示すモノマー単位比率およびグリシジルメタクリレートの比率を、仕込量を変えることで変更し、また重合体の反応時間を調整することで重量平均分子量を変更し、同様の操作を行い、高分子結合剤Ｂ、Ｃを得た。
【０１５８】
【表１】

【０１５９】
（支持体の作製）
厚さ０．２４ｍｍのアルミニウム板（材質１０５０、調質Ｈ１６）を６５℃に保たれた５％水酸化ナトリウム水溶液に浸漬し、１分間の脱脂処理を行った後、水洗した。この脱脂アルミニウム板を、２５℃に保たれた１０％塩酸水溶液中に１分間浸漬して中和した後、水洗した。次いで、このアルミニウム板を０．３質量％の塩酸水溶液中で、２５℃、電流密度１００Ａ／ｄｍ^２の条件下に交流電流により６０秒間、電解粗面化を行った後、６０℃に保たれた５％水酸化ナトリウム水溶液中で１０秒間のデスマット処理を行った。デスマット処理を行った粗面化アルミニウム板を１５％硫酸溶液中で、２５℃、電流密度１０Ａ／ｄｍ^２、電圧１５Ｖの条件下に１分間陽極酸化処理を行い、更に３％珪酸ナトリウムで９０℃で封孔処理を行って支持体を作製した。この時、表面の中心線平均粗さ（Ｒａ）は０．６５μｍであった。
【０１６０】
（支持体の表面処理）
上記作製したアルミニウム板を、８０℃の０．６％ポリビニルホスホン酸溶液中に３０秒間通し、イオン交換水で水洗後、乾燥した。
【０１６１】
《平版印刷版材料の作製》
上記表面処理済みアルミニウム板上に、下記組成の光重合性感光層塗工液を乾燥時１．５ｇ／ｍ^２になるようワイヤーバーで塗布し、９５℃で１．５分間乾燥した。その後、更に該感光層上に下記組成のオーバーコート層塗工液を乾燥時２．０ｇ／ｍ^２になるようにアプリケーターで塗布し、７５℃で１．５分間乾燥して、感光層上にオーバーコート層を有する平版印刷版材料を作製した。
【０１６２】

【０１６３】
【化１２】

【０１６４】
《画像形成》
このようにして作製した光重合型平版印刷版材料について、５３２ｎｍレーザー光源を搭載したＣＴＰ露光装置（Ｔｉｇｅｒｃａｔ：ＥＣＲＭ社製）を用いて２４００ｄｐｉ（ｄｐｉとは１インチ即ち２．５４ｃｍ当たりのドット数を表す）の解像度で画像露光を行った。次いで、現像前に加熱装置部、オーバーコート層を除去する前水洗部、下記現像液組成を充填した現像部、版面に付着した現像液を取り除く水洗部、画線部保護のためのガム液（ＧＷ−３：三菱化学社製を２倍希釈したもの）を備えたＣＴＰ自動現像機（ＰＨＷ２３−Ｖ：Ｔｅｃｈｎｉｇｒａｐｈ社製）で現像処理を行い、本発明１〜８及び比較１〜６の平版印刷版を得た。但し、加熱装置部分の電源は切り、加熱処理は露光後、セーフライト環境下に置いた別の加熱装置を用いて、表２の版面温度、加熱処理時間、風量、風速、露光後加熱までの経時時間となるように設定し熱処理を行った。
【０１６５】
現像液組成
Ａ珪酸カリ（珪酸カリウム） ８．０質量％
ペレックスＮＢＬ：花王（株）製 ３．０質量％
苛性カリ ｐＨ＝１２．３なるよう調整
《平版印刷版の評価》
上記のようにして得られた平版印刷版について、以下の評価をした。評価結果を表２に示す。
【０１６６】
（感度）
レーザーの露光エネルギーを変化させ、１００％ベタ画像濃度を露光エネルギー毎に測定し、最高ベタ濃度から−１０％の反射濃度の点を最低画像形成エネルギー＝感度とした。
【０１６７】
（耐刷１）
１７５線の画像を適性露光量で露光、現像して作製した平版印刷版を、印刷機（三菱重工業（株）製ＤＡＩＹＡ１Ｆ−１）で、コート紙、印刷インキ（東洋インク（株）製トーヨーキングハイエコーＭ紅）及び湿し水（東京インク（株）製Ｈ液ＳＧ−５１濃度１．５％）を用いて印刷を行い、ハイライト部の点が３％細る、又はシャドウ部の絡みの発生する印刷枚数を耐刷性の指標とした。
【０１６８】
（保存後汚れ）
平版印刷版材料を強制劣化させるため、５５℃、２０％の環境下の恒温槽に３日間保存し、保存する以前のサンプルと比較し、印刷汚れ評価を行い保存の影響を比較評価した。印刷は上記の耐刷１の記載条件で行い、刷り出し１００枚目のサンプルの非画像部を１００倍ルーペで観察し、非画像部５ｃｍ×５ｃｍにインク付着が２個以上ある場合を×、１個以下を○とした。
【０１６９】
結果を表２に示した。
【０１７０】
【表２】

【０１７１】
表２の結果から、本発明の版面温度、加熱処理時間、露光後経時、風量、風速が、感度、耐刷、保存性の観点で好ましいことがわかる。また、本発明のサンプルは保存での感度変動は見られなかった。
【０１７２】
実施例２
〔本発明９〜１６、比較７〜１４平版印刷版の作製〕
支持体の作製および表面処理は、実施例１同様に作製した。バインダーは上記で作製したものから選択して使用した。
【０１７３】
《平版印刷版材料の作製》
上記支持体上に、下記組成の光重合性感光層塗工液に変更した以外は、実施例１と同様の操作を行い、感光層上にオーバーコート層を有する平版印刷版材料を作製した。
【０１７４】

【０１７５】
【化１３】

【０１７６】
《画像形成》
このようにして作製した光重合型平版印刷版材料について、露光を、４０８ｎｍ、３０ｍＷ出力のレーザーを備えた光源を備えたプレートセッター（タイガーキャット：ＥＣＲＭ社製改造品）を用い、耐刷性評価時の露光量を８０μＪ／ｃｍ^２とした他は、実施例１と同様にして行った。２４００ｄｐｉの解像度で画像露光を行った。次いで、現像前に加熱装置部、オーバーコート層を除去する前水洗部、前記現像液組成を充填した現像部、版面に付着した現像液を取り除く水洗部、画線部保護のためのガム液（ＧＷ−３：三菱化学社製を２倍希釈したもの）を備えたＣＴＰ自動現像機（ＰＨＷ２３−Ｖ：Ｔｅｃｈｎｉｇｒａｐｈ社製）で現像処理を行い、本発明９〜１６及び比較７〜１４の平版印刷版を得た。
【０１７７】
このとき加熱装置部条件は、▲１▼電源ＯＦＦし、加熱なしで行ったもの、▲２▼版面温度１１５℃、版滞在時間１５秒となるように設定したものの２種作製した。また露光終了から自現機の加熱装置部への版挿入は６０秒以内に行った。
【０１７８】
（セーフライト：黄色）
イエロー蛍光灯（ＦＬ４０ＳＹ−ＩＣ、三菱電機オスラム株式会社製）を点灯しセーフライトとして用いた。照度計で測定した所、２５０Ｌｘであり、その環境で１分毎に照射時間を変化させ、現像不良を生じる時間を求めた。
【０１７９】
【表３】

【０１８０】
表３の結果で、各種感光層で加熱処理で性能向上が見られる。特に、本発明の好ましい素材を用いた系の性能向上が大きいことが伺える。また、加熱前後の感度の差が大きいほど、また光重合開始剤として鉄アレーンを用いるとき、セーフライト性が良好になる傾向も併せて見られる。更に、本発明は耐刷性とセーフライト性共に優れていることが分かる。また、本発明のサンプルは保存での感度変動は見られなかった。
【０１８１】
実施例３
〔本発明１７〜２５、比較１５〜１８平版印刷版の作製〕
次いでサンプルＮｏ．２６（本発明１２）の平版印刷版材料を用いて風量並びに風速を変化させ、本発明１７〜２５、比較１５〜１８の平版印刷版を得た。実施例１と同様に評価し、更に以下のインクでの耐刷評価を追加で評価した。
【０１８２】
（耐刷２）
１７５線の画像を適性露光量で露光、現像して作製した平版印刷版を印刷機（三菱重工業（株）製ＤＡＩＹＡ１Ｆ−１）で、コート紙、印刷インキ（大日本インキ化学工業社製、大豆油インキ“ナチュラリス１００”）及び湿し水（東京インク（株）製Ｈ液ＳＧ−５１濃度１．５％）を用いて印刷を行い、ハイライト部の点が３％細る、又はシャドウ部の絡みの発生する印刷枚数を耐刷性の指標とした。
【０１８３】
【表４】

【０１８４】
表４の結果で、本発明の好ましい感光層でも、本発明の版面温度、加熱処理時間、露光後経時の範囲で感度、耐刷、保存後汚れが良好になることがわかる。また、大豆多糖類インク（大日本インキ化学工業社製、大豆油インキ“ナチュラリス１００”）を用いた場合には、風量、風速の影響が大きくなることがわかる。また、本発明のサンプルは保存での感度変動は見られなかった。
【０１８５】
実施例４
〔本発明２６〜３３平版印刷版の作製〕
（支持体の作製）
厚さ０．２４ｍｍのアルミニウム板（材質１０５０、調質Ｈ１６）を６５℃に保たれた５％水酸化ナトリウム水溶液に浸漬し、１分間の脱脂処理を行った後、水洗した。この脱脂アルミニウム板を、２５℃に保たれた１０％塩酸水溶液中に１分間浸漬して中和した後、水洗した。次いで、このアルミニウム板を、０．３質量％の塩酸水溶液中で、２５℃、電流密度１００Ａ／ｄｍ^２の条件下に交流電流により６０秒間、電解粗面化を行った後、６０℃に保たれた５％水酸化ナトリウム水溶液中で１０秒間のデスマット処理を行った。デスマット処理を行った粗面化アルミニウム板を、１５％硫酸溶液中で、２５℃、電流密度１０Ａ／ｄｍ^２、電圧１５Ｖの条件下に１分間陽極酸化処理を行った。次いで、以下の各処理を行い、支持体を作製した。
【０１８６】
Ａ：アルミニウム板を８０℃の０．６％ポリビニルホスホン酸（ＰＶＰＡ）溶液中に３０秒間通し、イオン交換水で水洗後、乾燥した。
【０１８７】
Ｂ：アルミニウム板を９０℃の３％珪酸ナトリウム水溶液中に３０秒間通し、イオン交換水で水洗後、乾燥した。
【０１８８】
Ｃ：アルミニウム板を９０℃の１％リン酸塩水溶液中に３０秒間通し、イオン交換水で水洗後、乾燥した。
【０１８９】
Ｄ：アルミニウム板を８０℃のイオン交換水に３０秒間通し、乾燥した。
サンプル２６の条件で表５の支持体に夫々サンプル２６同様にして塗布し、オーバーコートもサンプル２６同様にして作製し、本発明２６〜３３平版印刷版を得た。
【０１９０】
評価結果を表５に示す。表５では、以下の保存での性能変動試験も行った。
（保存後汚れ）
光重合型平版印刷版材料を強制劣化させるため、５５℃、２０％の環境下の恒温槽に５日間保存し、保存する以前のサンプルと比較し、感度を評価した。更には、保存後汚れ評価を実施例１と同様にして行い、保存の影響を比較評価した。
【０１９１】
【表５】

【０１９２】
表５より、感度、耐刷性、汚れが良好であるのは言うまでもないが、特に支持体Ｒａ、親水化処理を変更することで性能上好ましい態様が確認できる。支持体Ｒａとしては、０．２〜０．７μｍ、特に好ましくは０．５〜０．７μｍであり、親水化処理としては、ＰＶＰＡ処理が好ましいことがわかる。また、いずれもセーフライト性は良好であった。
【０１９３】
実施例５
〔本発明３４〜３６平版印刷版の作製〕
サンプル２６の感材を用い、下記現像液で本発明３４〜３６の平版印刷版を得た。同様に性能評価した。
【０１９４】
現像液組成
Ａ珪酸カリ ８．０質量％
表６に示す現像活性剤 ５．０質量％
苛性カリ ｐＨ＝１２．３となる添加量
結果を表６に記載する。
【０１９５】
【表６】

【０１９６】
【化１４】

【０１９７】
表６より、好ましい現像活性剤を組み合わせると、セーフライト性が良好になることがわかる。
【０１９８】
【発明の効果】
本発明によって、高感度で、明室取扱い性、耐刷性共に優れ、且つ平版印刷版材料としての保存性に優れた平版印刷版の製版方法、及びその製法にて作製された平版印刷版を提供することができた。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for making a lithographic printing plate compatible with laser exposure and a lithographic printing plate produced thereby.
[0002]
[Prior art]
Generally, in a lithographic printing plate, after image exposure, an exposed portion is cured and an unexposed portion is dissolved and removed, followed by washing with water and finisher gum treatment to obtain a lithographic printing plate. In recent years, in order to obtain high resolving power and sharpness, a method for producing a lithographic printing plate by performing digital exposure with a laser beam based on image information and developing it has been studied. For example, a system for producing a lithographic printing plate by modulating an exposure light source by an image signal transmitted through a communication line, an output signal from an electronic plate making system, an image processing system, etc., and performing direct scanning exposure on a photosensitive material. It is.
[0003]
However, a conventional lithographic printing plate material using a diazo resin has a problem that it is difficult to achieve spectral sensitization and high sensitivity in accordance with the oscillation wavelength of laser light by digital exposure.
[0004]
In recent years, a lithographic printing plate material having a photopolymerizable photosensitive layer containing a photopolymerization initiator has been attracting attention for digital exposure using laser light because it can achieve high sensitivity suitable for laser light. A CTP (Computer To Plate) plate material for recording digital data with this laser light source is required to have high sensitivity in order to shorten the recording time. In addition, printing materials having printing durability are required in many printing fields including newspaper printing and commercial printing such as advertisements.
[0005]
It is known that printing durability is improved by heating after exposure. Up to now, development stability has been improved as a result of introducing preheating, support elongation / warping problems due to heat, and differences in support thickness. There are various problems for improving the fog.
[0006]
A technique of performing heat treatment at 50 to 180 ° C. for 5 seconds to 10 minutes after exposure (for example, see Patent Document 1), a technique of performing heat treatment at 36 to 48 ° C. for 10 seconds to 3 minutes after exposure with visible laser light. (For example, refer to Patent Document 2.) After heating, a technique of heating and cooling to a liquid temperature or lower before immersion in a developing solution (for example, refer to Patent Document 3). -Washing-Development of a technique (for example, see Patent Document 4) in which the difference between the washing liquid and the plate surface temperature immediately before washing is within 70 ° C. has been disclosed, but both techniques sufficiently solve the problem. It's hard to say.
[0007]
In recent years, along with the development of semiconductor lasers, exposure machines equipped with semiconductor lasers in the near ultraviolet region have been announced. These exposure machines are attracting a great deal of attention from the viewpoint of cost / maintenance, and handling of a bright room not found in visible light photopolymers. However, at present, the output of the semiconductor laser is about 30 mw, and the light room handling property of the light-sensitive material corresponding to the output is extremely insufficient. Furthermore, the storability of the lithographic printing plate material is still insufficient.
[0008]
[Patent Document 1]
Japanese Unexamined Patent Publication No. 57-119343
[0009]
[Patent Document 2]
JP-A-10-26834
[0010]
[Patent Document 3]
JP-A-8-286388
[0011]
[Patent Document 4]
JP 2002-278086 A
[0012]
[Problems to be solved by the invention]
Accordingly, the object of the present invention is a plate-making method of a lithographic printing plate having high sensitivity, bright room handling property (hereinafter also referred to as safelight property), excellent printing durability, and excellent storability as a lithographic printing plate material, And providing a lithographic printing plate produced by the method.
[0013]
[Means for Solving the Problems]
The above object of the present invention has been achieved by the following constitution.
[0014]
1) After image exposure to a lithographic printing plate material in which a polymerizable compound having an ethylenically unsaturated group, a photopolymerization initiator, a photosensitive layer containing a sensitizing dye, and an oxygen blocking layer are provided in this order on an aluminum support, A plate making method of a lithographic printing plate, wherein the plate surface temperature is 80 to 150 ° C. within 10 minutes and heat treatment is performed for 5 seconds to 3 minutes, followed by development.
[0015]
2) The plate making method of a lithographic printing plate as described in 1) above, wherein the wind speed with respect to the plate surface during heating is 0.1 to 50 m / s.
[0016]
3) Air volume during heating is 5 to 200m ³ The plate making method of a lithographic printing plate as described in 1) or 2) above, wherein
[0017]
4) The plate making method of a lithographic printing plate as described in any one of 1) to 3) above, wherein the image exposure is image exposure with a laser having a wavelength of 450 nm or less.
[0018]
5) Any of 1) to 4) above, wherein 10 to 90% by mass of the polymerizable compound having an ethylenically unsaturated group is a weight average molecular weight of 15,000 to 500,000 and an acid value of 30 to 200 mg / KOH. 2. A method for making a lithographic printing plate as described in 1 above.
[0019]
6) Any of 1) to 4) above, wherein 20 to 70% by mass of the polymerizable compound having an ethylenically unsaturated group is a weight average molecular weight of 25,000 to 200,000 and an acid value of 60 to 180 mg / KOH. 2. A method for making a lithographic printing plate as described in 1 above.
[0020]
7) The above-described 5) or 6), wherein the polymerizable compound having an ethylenically unsaturated group has a repeating unit, and the unit ratio of the reactive group contained in the repeating unit is 5 to 50%. ).
[0021]
8) Any one of the above 1) to 7), wherein the polymerizable compound having an ethylenically unsaturated group contains a polyfunctional acrylate having an amide bond and a secondary or tertiary amine group in one molecule. A process for making a lithographic printing plate as described in the paragraph.
[0022]
9) The sensitizing dye has at least one skeleton among coumarins, ketocoumarins, oxonols, barbituric acids, pyromethene borates, and dyes having a diphenylmethane skeleton, any one of the above 1) to 8) A process for making a lithographic printing plate as described in 1.
[0023]
10) The lithographic printing according to any one of 1) to 9) above, wherein the photopolymerization initiator contains at least one of a titanocene compound, a metal arene compound, and a monoalkyltriarylborate compound. Plate making method.
[0024]
11) The plate making method of a lithographic printing plate as described in 10) above, wherein the metal arene compound is an iron arene compound.
[0025]
12) The above-mentioned 1) to 11), wherein the aluminum support is a support having an electrically roughened aluminum plate in an acid medium and an anodized surface Ra of 0.2 to 0.7 μm. The plate making method of a lithographic printing plate as described in any one of (1).
[0026]
13) The above-mentioned 1) to 11), wherein the aluminum support is a support having an aluminum plate electrically roughened in an acid medium and an anodized surface Ra of 0.5 to 0.7 μm. The plate making method of a lithographic printing plate as described in any one of (1).
[0027]
14) The plate-making method of a lithographic printing plate as described in 12) or 13) above, which comprises a post-treatment step after anodization and the post-treatment is PVPA treatment.
[0028]
15) The plate making method of a lithographic printing plate as described in any one of 1) to 14) above, wherein the developer used in the development treatment is an alkaline developer having a pH of 10 to 12.5.
[0029]
16) The alkali developer containing an inorganic alkali agent and a nonionic surfactant having a polyoxyalkylene ether group, having a pH of 10.0 to 12.5 and a conductivity of 3 to 30 mS / cm A method for making a lithographic printing plate as described in 15).
[0030]
17) The alkaline developer containing an inorganic alkaline agent and an anionic surfactant having a polyoxyalkylene ether group, having a pH of 10.0 to 12.5 and a conductivity of 3 to 30 mS / cm A method for making a lithographic printing plate as described in 15).
[0031]
18) The plate making method of a lithographic printing plate as described in 16) or 17) above, wherein the addition amount of the surfactant is 1.5 to 8% by mass.
[0032]
19) A lithographic printing plate produced by the lithographic printing plate making method according to any one of 1) to 18) above.
[0033]
Hereinafter, the present invention will be described in detail.
In the present invention, the heat treatment after exposure but before development processing is also referred to as preheating. The preheat of the present invention is preferably processed within 10 minutes after exposure. The preferred photosensitive layer of the present invention is characterized by low image-forming ability only by exposure, and further uses a highly soluble developer. It is preferable that the performance obtained only by exposure is low.
[0034]
Specifically, the ratio between the sensitivity obtained by the method described in Examples obtained only by exposure and the sensitivity obtained by exposure and heat treatment is 1.2: 1 to 50: 1, preferably 1.5: 1. 40: 1, particularly preferably 2.5: 1 to 30: 1. By designing the lithographic printing plate material / developer and plate making method in this way, the safe light property is improved, and in particular, a laser of 450 nm or less. In the system corresponding to the exposure apparatus, the safe light property can be dramatically improved.
[0035]
As described above, in the present invention, active radicals are generated by exposure, the growth reaction is accelerated by heat treatment, and the degree of cross-linking is drastically improved, so that the printing durability is strongly expressed. For this reason, when the elapsed time after exposure is remarkably longer than 10 minutes, the deactivation of the active species becomes remarkable, and the printing durability tends to deteriorate.
[0036]
In order to obtain good printing durability, it is preferable to perform heat treatment at a plate surface temperature of 80 to 150 ° C., more preferably 90 to 140 ° C., and particularly preferably 100 to 130 ° C. The plate surface temperature at the time of heating is particularly preferably a temperature equal to or higher than Tg of a polymerizable compound having an ethylenically unsaturated group having a weight average molecular weight of 15000 or more contained in the lithographic printing plate material, and is 10 ° C. or higher than Tg Is more preferable, and particularly preferably 20 ° C. or higher. If the plate surface temperature is extremely high from the range of the present invention, the load on the apparatus increases, which is not preferable. Conversely, if the plate surface temperature is extremely low, the printing durability tends to deteriorate.
[0037]
Further, the heating time is preferably 5 seconds to 3 minutes, more preferably 5 seconds to 1 minute, particularly preferably 5 seconds to 30 seconds. If the heating time is extremely long from the scope of the present invention, it is not preferable in actual work. Conversely, if the heating time is extremely short, the stability tends to deteriorate.
[0038]
The wind speed with respect to the plate surface during heating is preferably 0.1 to 50 m / s, more preferably 1 to 30 m / s, and particularly preferably 5 to 20 m / s. When the wind speed is significantly higher than the range of the present invention, the load on the apparatus is increased and the transportability is also deteriorated, which is not preferable. On the other hand, when the wind speed is significantly decreased, the plate temperature rises slowly and the stability of performance tends to deteriorate. . Moreover, the air volume at the time of heating, more specifically, the air volume of the heat treatment unit is 5 to 200 m. ³ / H is preferred, 10 to 100 m ³ / H is more preferable, 25-70m ³ / H is particularly preferred. If the air volume is significantly increased from the scope of the present invention, the load on the apparatus increases, which is not preferable. On the other hand, when it becomes extremely small, the stability of performance tends to deteriorate.
[0039]
(Polymerizable compound having an ethylenically unsaturated group)
As the polymerizable compound having an ethylenically unsaturated group of the present invention, a conventionally known compound having a monofunctional or polyfunctional ethylenically unsaturated group can be suitably used.
[0040]
In the present invention, 1) a polymerizable compound having an ethylenically unsaturated group has a weight average molecular weight of 15,000 to 500,000 and an acid value of 30 to 200 mg / KOH, and 2) has an ethylenically unsaturated group. Either use, wherein the polymerizable compound is a polyfunctional acrylate having an amide bond and a secondary or tertiary amino group in one molecule.
[0041]
One form of the polymerizable compound having an ethylenically unsaturated group that is more preferably used in the present invention is a compound having a weight average molecular weight of 25,000 to 200,000 and an acid value of 60 to 180 mg / KOH. is there. The weight average molecular weight is a value measured by gel permeation chromatography (GPC).
[0042]
As long as it is a polymerizable compound having such a high molecular weight ethylenically unsaturated group, any conventionally known resin skeleton can be used. Among these, acrylic resins, urethane resins, polyester resins, and phenol resins are preferable, and acrylic resins are particularly preferable.
[0043]
As for the method of introducing an ethylenically unsaturated group into the acrylic resin, a known method can be used without limitation. For example, the method of making a glycidyl group react with the below-mentioned carboxyl group, the method of making an isocyanate group react with a hydroxyl group, etc. can be mentioned.
[0044]
Specifically, for example, allyl glycidyl ether, glycidyl (meth) acrylate, α-ethylglycidyl (meth) acrylate, glycidyl crotonate, glycidyl isocrotonate, crotonyl are used as the copolymer having a monomer unit having a carboxyl group. Aliphatic epoxy group-containing unsaturated compounds such as glycidyl ether, monoalkyl monoglycidyl itaconate, monoalkyl monoglycidyl fumarate, monoalkyl monoglycidyl maleate, or 3,4-epoxycyclohexylmethyl (meth) acrylate It is a reaction product obtained by reacting an alicyclic epoxy group-containing unsaturated compound such as the above with the carboxyl group.
[0045]
In the present invention, the reactive group in the unit ratio having a reactive group refers to an ethylenically unsaturated group having radical polymerizability, and specifically refers to a vinyl group, an aryl group, a (meth) acryloyl group, and the like. Of these, a (meth) acryloyl group is preferable.
[0046]
The unit ratio refers to, for example, mol% in which the carboxyl group and the epoxy group-containing unsaturated compound are reacted. In the present invention, the reacted unit is preferably 5 to 50 mol%, particularly preferably 10 to 30 mol%. It is. If it is less than 5 mol%, the sensitivity and printing durability are insufficient, and if it is more than 50 mol%, the storage stability of the material itself tends to deteriorate, which is not preferred.
[0047]
In the present invention, the acid value is the number of mg of potassium hydroxide necessary to neutralize 1 g of the compound. The acid value can be measured as follows. The sample is diluted 50 times with methyl cellosolve and titrated with 0.1 mol / L potassium hydroxide. The inflection point of the pH curve obtained using a pH meter is taken as the neutralization point. The acid value is calculated from the amount of potassium hydroxide required to reach this neutralization point.
[0048]
Reaction of the copolymer which has a monomer unit which has a carboxyl group, and an epoxy-group-containing unsaturated compound can be made to react at the temperature of about 80-120 degreeC, and about 1 to 50 hours, for example. As a synthesis method of the reaction product, it can be synthesized by a generally known polymerization method. R. Sorenson, T.W. W. It can be synthesized according to a method described in a literature such as Campbell, the methods described in JP-A Nos. 10-315598 and 11-271963, and the like.
[0049]
The addition amount of the polymerizable compound having a high molecular weight ethylenically unsaturated group is preferably 10 to 90% by mass, preferably 20 to 70% by mass, based on the total amount of the polymerizable compound having an ethylenically unsaturated group. Is more preferable. When the amount is less than 10% by mass or more than 90% by mass, both sensitivity and printing durability are deteriorated, which is not preferable.
[0050]
The copolymer having a monomer unit having a carboxyl group is preferably a vinyl copolymer having a monomer unit of an α, β-unsaturated carboxylic acid described in the following (5) as a constituent element. It is also preferable to contain a vinyl copolymer comprising at least one of the monomers (1) to (17).
[0051]
(1) Monomer having an aromatic hydroxyl group
(2) Monomers having an aliphatic hydroxyl group
(3) Monomer having an aminosulfonyl group
(4) Monomer having a sulfonamide group
(5) α, β-unsaturated carboxylic acids
(6) Substituted or unsubstituted alkyl acrylate
(7) substituted or unsubstituted alkyl methacrylate
(8) Acrylamide or methacrylamide
(9) Monomer containing alkyl fluoride group
(10) Vinyl ethers
(11) Vinyl esters
(12) Styrenes
(13) Vinyl ketones
(14) Olefins
(15) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, etc.
(16) Monomer having a cyano group
(17) Monomer having an amino group
Specific examples of the compound include 2-ethylhexyl acrylate, 2-hydroxypropyl acrylate, glycerol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, nonylphenoxyethyl acrylate, tetrahydrofurfuryloxyethyl acrylate, tetrahydrofurfuryloxyhexanol. Acrylates, acrylates of ε-caprolactone adducts of 1,3-dioxane alcohol, monofunctional acrylic esters such as 1,3-dioxolane acrylate, or methacrylic acid in which these acrylates are replaced with methacrylate, itaconate, crotonate, or maleate , Itaconic acid, crotonic acid, maleic acid ester; for example, ethylene glycol diacrylate, triethylene Of glycol diacrylate, pentaerythritol diacrylate, hydroquinone diacrylate, resorcin diacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, dipentylate of neopentyl glycol hydroxypivalate, neopentyl glycol adipate Diacrylate, diacrylate of ε-caprolactone adduct of neopentyl glycol hydroxypivalate, 2- (2-hydroxy-1,1-dimethylethyl) -5-hydroxymethyl-5-ethyl-1,3-dioxane diacrylate , Tricyclodecane dimethylol acrylate, ε-caprolactone adduct of tricyclodecane dimethylol acrylate, 1,6-hexane Difunctional acrylates such as diacrylate of all diglycidyl ethers, or methacrylic acid, itaconic acid, crotonic acid, maleic acid ester in which these acrylates are replaced with methacrylate, itaconate, crotonate, maleate; Acrylates, ditrimethylolpropane tetraacrylate, trimethylolethane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, ε- of dipentaerythritol hexaacrylate Caprolactone adduct, pyrogallol triacrylate, propion・ Multifunctional acrylic acid esters such as dipentaerythritol triacrylate, propionic acid, dipentaerythritol tetraacrylate, hydroxypivalylaldehyde-modified dimethylolpropane triacrylate, and their EO-modified products, or their acrylates as methacrylates and itaconates , Methacrylic acid, itaconic acid, crotonic acid, maleic acid ester, etc., instead of crotonate and maleate.
[0052]
Prepolymers can also be used as described above. Examples of the prepolymer include compounds as described below, and a prepolymer obtained by introducing acrylic acid or methacrylic acid into an oligomer having an appropriate molecular weight and imparting photopolymerizability can be suitably used. These prepolymers may be used alone or in combination of two or more, or may be used in admixture with the aforementioned monomers or oligomers.
[0053]
Examples of the prepolymer include adipic acid, trimellitic acid, maleic acid, phthalic acid, terephthalic acid, hymic acid, malonic acid, succinic acid, glutaric acid, itaconic acid, pyromellitic acid, fumaric acid, glutaric acid, and pimelic acid. , Polybasic acids such as sebacic acid, dodecanoic acid, tetrahydrophthalic acid, and ethylene glycol, propylene glycol, diethylene glycol, propylene oxide, 1,4-butanediol, triethylene glycol, tetraethylene glycol, polyethylene glycol, glycerin, tri Polyester obtained by introducing (meth) acrylic acid into a polyester obtained by combining polyhydric alcohols such as methylolpropane, pentaerythritol, sorbitol, 1,6-hexanediol, 1,2,6-hexanetriol Acrylates, for example, bisphenol A, epichlorohydrin, (meth) acrylic acid, and epoxy acrylates in which (meth) acrylic acid is introduced into an epoxy resin such as phenol novolac, epichlorohydrin, (meth) acrylic acid; Acid / tolylene diisocyanate / 2-hydroxyethyl acrylate, polyethylene glycol / tolylene diisocyanate / 2-hydroxyethyl acrylate, hydroxyethylphthalyl methacrylate / xylene diisocyanate, 1,2-polybutadiene glycol / tolylene diisocyanate / 2-hydroxyethyl acrylate , Trimethylolpropane, propylene glycol, tolylene diisocyanate, 2-hydroxyethyl acrylate As described above, urethane acrylates in which (meth) acrylic acid is introduced into urethane resins; for example, silicone resin acrylates such as polysiloxane acrylate, polysiloxane diisocyanate, 2-hydroxyethyl acrylate; and (meth) in oil-modified alkyd resins Examples thereof include prepolymers such as alkyd-modified acrylates and spirane resin acrylates into which acryloyl groups are introduced.
[0054]
The photosensitive layer of the lithographic printing plate material according to the present invention includes a phosphazene monomer, triethylene glycol, isocyanuric acid EO (ethylene oxide) -modified diacrylate, isocyanuric acid EO-modified triacrylate, dimethylol tricyclodecane diacrylate, and trimethylol. It can contain monomers such as propaneacrylic acid benzoate, alkylene glycol type acrylic acid-modified, urethane-modified acrylate, and addition polymerizable oligomers and prepolymers having structural units formed from the monomers.
[0055]
Furthermore, examples of the polymerizable compound having an ethylenically unsaturated group used in the present invention include a phosphoric acid ester compound containing at least one (meth) acryloyl group. The compound is not particularly limited as long as it is a compound in which at least part of the hydroxyl group of phosphoric acid is esterified and has a (meth) acryloyl group.
[0056]
In addition, JP-A-58-212994, 61-6649, 62-46688, 62-48589, 62-173295, 62-187092, 63 -67189, JP-A-1-244891, and the like. Further, "11290 Chemical Products", Chemical Industry Daily, pages 286-294, "UV / EB Curing" The compounds described in “Handbook (raw material)”, Kobunshi Shuppankai, pages 11 to 65, and the like can also be suitably used. Of these, compounds having two or more acrylic groups or methacryl groups in the molecule are preferred in the present invention, and those having a molecular weight of 10,000 or less, more preferably 5,000 or less are preferred.
[0057]
Here, a compound having an amide bond and a secondary or tertiary amino group in one molecule, which is particularly preferably used in the present invention, is represented by the following general formula (1).
[0058]
[Chemical 1]

[0059]
Where Q ¹ Is
[0060]
[Chemical 2]

[0061]
Or -S-, R ⁴ Represents an alkyl group, a hydroxyalkyl group or an aryl group, R ¹ And R ² Each represents a hydrogen atom, an alkyl group or an alkoxyalkyl group; ³ Represents a hydrogen atom, a methyl group or an ethyl group, and X ¹ Represents a divalent group having 2 to 12 carbon atoms, X ² Is a divalent group to a tetravalent group, or
[0062]
[Chemical 3]

[0063]
Z represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a halogen atom, an alkoxyl group or a heterocyclic group, p represents an integer of 1 to 4, and q represents an integer of 1 to 3. D ¹ And D ² Each represents a divalent group having 1 to 5 carbon atoms, E is a divalent group having 2 to 12 carbon atoms, a 5- to 7-membered ring, and a nitrogen atom, oxygen atom and sulfur An aliphatic group having a heterocyclic ring containing one or two atoms selected from the group consisting of atoms, an arylene group having 6 to 12 carbon atoms, or an aromatic heterocyclic group having a 5 or 6 membered ring. A represents 0 or an integer of 1 to 4, b represents 0 or 1, c represents an integer of 1 to 3, and m represents Q ¹ Represents an integer of 2 to 4, and n represents an integer of 1 to m, and a plurality of groups having the same definition may be the same or different from each other.
[0064]
In the general formula (1), R ⁴ As the alkyl group represented by, for example, methyl, ethyl, propyl, butyl, pentyl, i-pentyl, 2-ethylhexyl, octyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, docosadecyl, etc. Each group is mentioned.
[0065]
R ⁴ Examples of the hydroxyalkyl group represented by the formula include hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxypentyl and the like.
[0066]
Also, R ⁴ Examples of the aryl group represented by the formula include groups such as phenyl and naphthyl.
[0067]
R ¹ And R ² The alkyl group represented by ⁴ It is synonymous with the alkyl group represented by these.
[0068]
R ¹ And R ² Examples of the alkoxyalkyl group represented by the formula include groups such as methoxymethyl, methoxyethyl, ethoxymethyl, and propoxyethyl.
[0069]
X ¹ Examples of the divalent group having 2 to 12 carbon atoms represented by the formula include a saturated hydrocarbon group and an arylene group. X ¹ Examples of the saturated hydrocarbon group having 2 to 12 carbon atoms represented by: ethylene, trimethylene, tetramethylene, propylene, ethylethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undeca Examples include methylene, dodecamethylene, cyclohexylene (1,6-cyclohexanediyl, etc.), cyclopentylene (1,5-cyclopentanediyl, etc.), and the like.
[0070]
X ¹ Examples of the arylene group represented by the formula include groups such as phenylene and naphthylene.
[0071]
X ² The divalent group represented by ¹ Saturated hydrocarbon group, arylene group, etc. mentioned as a divalent group having 2 to 12 carbon atoms represented by the above can be used, and further up to 5 methylene in the saturated hydrocarbon group Those in which the group is substituted with an oxygen atom can be used.
[0072]
X ² The trivalent group represented by ² And a divalent group (saturated hydrocarbon group, arylene group, etc.) with one additional linking group, ethanetriyl, propanetriyl, butanetriyl, pentanetriyl, hexanetriyl, heptanetriyl , Octanetriyl, nonanetriyl, decanetriyl, undecanetriyl, dodecanetriyl, cyclohexanetriyl, cyclopentanetriyl, benzenetriyl, naphthalenetriyl, and the like.
[0073]
X ² The tetravalent group represented by X is the above X ² In addition, one linking group is added to the trivalent group represented by propanediylidene, 1,3-propanediyl-2-ylidene, butanediylidene, pentanediylidene, hexanediylidene, heptanediylidene, Examples include octanediylidene, nonanediylidene, decandiylidene, undecandiylidene, dodecandiylidene, cyclohexanediylidene, cyclopentanediylidene, benzenetetrayl, naphthalenetetrayl, and the like.
[0074]
Examples of the alkyl group represented by Z include groups such as methyl, ethyl, propyl, butyl, pentyl, i-pentyl, 2-ethylhexyl, octyl, and decyl.
[0075]
Examples of the alkenyl group represented by Z include 2-propenyl, 3-butenyl, 1-methyl-3-propenyl, 3-pentenyl, 1-methyl-3-butenyl, 4-hexenyl and the like. Examples of the aryl group represented by Z include phenyl, m-chlorophenyl, p-tolyl, naphthyl and the like.
[0076]
Examples of the halogen atom represented by Z include fluorine, chlorine, bromine and iodine.
[0077]
Examples of the alkoxyl group represented by Z include methoxy, ethoxy, propoxy, butoxy and the like.
[0078]
Examples of the heterocyclic group represented by Z include groups such as pyridyl, pyrrolyl, 2-methylpyrrolyl, indolyl, imidazolyl, furyl, thiazolyl, and pyrimidinyl.
[0079]
D ¹ And D ² Examples of the divalent group having 1 to 5 carbon atoms represented by: methylene, trimethylene, tetramethylene, propylene, ethylethylene, pentamethylene, cyclopentylene, and the like.
[0080]
The divalent group having 2 to 12 carbon atoms represented by E is X ¹ It is synonymous with the bivalent group which has 2-12 carbon atoms represented by these.
[0081]
A 5- to 7-membered ring represented by E and an aliphatic group having a heterocyclic ring containing one or two atoms selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom as a substituent. Heterocycles include pyridine, furan, pyrrole, pyrazole, imidazole, oxazole, thiazole, pyrimidine, pyridazine, pyran, thiophene, isoxazole, pyrroline, imidazoline, imidazolidine, pyrazolidine, pyrazoline, piperidine, piperazine, morpholine, quinuclidine, etc. Each ring is mentioned.
[0082]
Examples of the aliphatic group include divalent groups having 2 to 12 carbon atoms having the above-described heterocyclic ring, and the divalent group includes X ¹ It is synonymous with the bivalent group which has 2-12 carbon atoms represented by these.
[0083]
Examples of the arylene group having 6 to 12 carbon atoms represented by E include groups such as phenylene and naphthylene.
[0084]
Examples of the aromatic heterocyclic ring constituting the aromatic heterocyclic group having a 5- or 6-membered ring represented by E include furan, pyrrole, pyrazole, imidazole, oxazole, thiazole, 1,2,3-oxadiazole, 1 , 2,3-triazole, 1,2,4-triazole, 1,3,4-thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, s-triazine, benzofuran, indole, benzothiophene, benzimidazole, benzothiazole, purine, Examples of the ring include quinoline and isoquinoline.
[0085]
Each substituent represented by the general formula (1) may further have a substituent.
The compound represented by the general formula (1) can be synthesized by referring to a method well known to those skilled in the art, for example, the method described in US Pat. No. 2,509,288.
[0086]
Hereinafter, although the specific example of a compound represented by General formula (1) is given, this invention is not limited to these.
[0087]
[Formula 4]

[0088]
[Chemical formula 5]

[0089]
[Chemical 6]

[0090]
A compound containing an ethylenically unsaturated group represented by the following general formula (2) is also preferred.
[0091]
[Chemical 7]

[0092]
Where Q ² Is
[0093]
[Chemical 8]

[0094]
Represents R ⁸ Represents an alkyl group, a hydroxyalkyl group or an aryl group, R ⁵ And R ⁶ Each represents a hydrogen atom, an alkyl group or an alkoxyalkyl group; ⁷ Represents a hydrogen atom, a methyl group or an ethyl group, and D ³ And D ⁴ Each represents a saturated hydrocarbon group having 1 to 5 carbon atoms, F is a saturated hydrocarbon group having 2 to 12 carbon atoms, a 5- to 7-membered ring, and up to 2 N, O or A cyclic aliphatic group containing an S atom as a member ring, an arylene group having 6 to 12 carbon atoms, or a heterocyclic aromatic group having a 5 to 6 member ring, d and e are integers of 1 to 4 And g is Q ² Represents an integer of 2 to 4, and f represents an integer of 1 to g, and a plurality of groups having the same definition may be the same or different from each other.
[0095]
In the general formula (2), R ⁸ May be different from each other when (g−f) is 2 or more. Compounds in which g and f are the same value are preferred. R ⁸ Is an alkyl group or a hydroxyalkyl group, it preferably has 2 to 8 carbon atoms, more preferably 2 to 4 carbon atoms. R ⁸ When is an aryl group, a monocyclic ring or bicyclic ring is preferable, a monocyclic ring is more preferable, and an alkyl group, alkoxyalkyl group or halogen atom having up to 5 carbon atoms may be substituted.
[0096]
R ⁵ And R ⁶ When is an alkyl group or an alkoxyalkyl group, C1-C5 is preferable. R ⁷ Is preferably a methyl group.
[0097]
D ³ And D ⁴ May be the same or different and are preferably 6-membered saturated heterocycles containing two nitrogen atoms.
[0098]
When F is a saturated hydrocarbon group, it preferably has 2 to 6 carbon atoms. When F is an arylene group, a phenylene group is preferable. When F is a cyclic aliphatic group, a cyclohexylene group is preferable. In the case of a group, a 5- or 6-membered ring containing a nitrogen atom or a sulfur atom is preferable.
[0099]
To obtain the compound represented by the general formula (2), Q ² Is N and g and f have the same value, glycidyl acrylate or alkyl acrylate is reacted with hydroxyalkylamine. Other compounds can be obtained in the same manner.
[0100]
Specific examples of the compound represented by the general formula (2) are shown below.
[0101]
[Chemical 9]

[0102]
The photosensitive layer of the lithographic printing plate material according to the present invention preferably contains the above-described polymerizable compound containing an ethylenically unsaturated group in a range of 5 to 99% by mass, preferably 10 to 98% by mass. Is more preferable, and a range of 20 to 97% by mass is particularly preferable.
[0103]
(Photopolymerization initiator)
The photopolymerization initiator is a compound that initiates polymerization of a polymerizable compound containing an ethylenically unsaturated group, and examples thereof include titanocene compounds, metal arene compounds, and monoalkyltriaryl borate compounds. Among these, a metal arene compound is preferable, and is represented by the following structural formula.
[0104]
Embedded image

[0105]
In the formula, M is a metal atom such as iron, nickel or cobalt, X ⁻ Is BF ^4- , PF ^6- , AsF ^6- , SbF ^6- A basic ion such as Y represents a group containing at least one benzene ring.
[0106]
Desirable metal arene compounds are iron arene compounds, chromium arene compounds, manganese arene compounds, cobalt arene compounds, nickel arene compounds, etc. Among them, the use of iron arene compounds can further improve sensitivity. preferable.
[0107]
Examples of the iron arene compound include compounds described in JP-A-59-219307, and more preferable specific examples include η-benzene- (η-cyclopentadienyl) iron / hexafluorophosphate, η -Cumene- (η-cyclopentadienyl) iron / hexafluorophosphate, η-fluorene- (η-cyclopentadienyl) iron / hexafluorophosphate, η-naphthalene- (η-cyclopentadienyl) iron / hexa Fluorophosphate, η-xylene- (η-cyclopentadienyl) iron • hexafluorophosphate, η-benzene- (η-cyclopentadienyl) iron • tetrafluoroborate and the like.
[0108]
Examples of the titanocene compound include compounds described in JP-A-63-41483 and JP-A-2-291. More preferable specific examples include bis (cyclopentadienyl) -Ti-di. -Chloride, bis (cyclopentadienyl) -Ti-bis-phenyl, bis (cyclopentadienyl) -Ti-bis-2,3,4,5,6-pentafluorophenyl, bis (cyclopentadienyl) -Ti-bis-2,3,5,6-tetrafluorophenyl, bis (cyclopentadienyl) -Ti-bis-2,4,6-trifluorophenyl, bis (cyclopentadienyl) -Ti-bis -2,6-difluorophenyl, bis (cyclopentadienyl) -Ti-bis-2,4-difluorophenyl, bis (methylcyclopentadienyl)- i-bis-2,3,4,5,6-pentafluorophenyl, bis (methylcyclopentadienyl) -Ti-bis-2,3,5,6-tetrafluorophenyl, bis (methylcyclopentadienyl) ) -Ti-bis-2,6-difluorophenyl (IRUGACURE 727L: manufactured by Ciba Specialty Chemicals), bis (cyclopentadienyl) -bis (2,6-difluoro-3- (py-1-yl) phenyl) titanium (IRUGACURE784: manufactured by Ciba Specialty Chemicals), bis (cyclopentadienyl) -bis (2,4,6-trifluoro-3- (pyridin-1-yl) phenyl) titanium bis (cyclopentadienyl) -bis (2,4,6-trifluoro-3- (2-5-dimethylpy-1-yl) phenyl) titani Beam, and the like.
[0109]
Examples of the monoalkyl triaryl borate compound include compounds described in JP-A Nos. 62-150242 and 62-143044, and more preferable specific examples include tetrabutylammonium butyl-trinaphthalene. -1-yl-borate, tetrabutylammonium butyl-triphenylborate, tetrabutylammonium butyl-tri (4-t-butylphenyl) borate, tetrabutylammonium hexyl-tri (3-chloro-4-methylphenyl) ) Borate, tetrabutylammonium hexyl-tri (3-fluorophenyl) borate and the like.
[0110]
Furthermore, J. et al. Examples include carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, and photoreductive dyes as described in Chapter 5 of “Light Sensitive Systems” by J. Kosar. It is done. More specific compounds are disclosed in GB 1,459,563. That is, as the photopolymerization initiator that can be used in combination, the following can be used.
[0111]
Benzoin derivatives such as benzoin methyl ether, benzoin-i-propyl ether, α, α-dimethoxy-α-phenylacetophenone; benzophenone, 2,4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4,4′-bis (dimethyl) Benzophenone derivatives such as amino) benzophenone; thioxanthone derivatives such as 2-chlorothioxanthone and 2-i-propylthioxanthone; anthraquinone derivatives such as 2-chloroanthraquinone and 2-methylanthraquinone; N-methylacridone, N-butylacridone and the like In addition to α, α-diethoxyacetophenone, benzyl, fluorenone, xanthone and uranyl compounds, JP-B-59-1281, JP-A-61-9621 and JP-A-60-60104 Triazine derivatives described in Japanese Patent Publication No. JP-A-59-1504 and JP-A-61-243807; JP-B Nos. 43-23684, 44-6413, 44-6413 47-1604 and U.S. Pat. No. 3,567,453; diazonium compounds; U.S. Pat. Nos. 2,848,328, 2,852,379 and 2,940,853. Organic azide compounds described in Japanese Patent Publication No. 36-22062b, 37-13109, 38-18015, and 45-9610; o-quinonediazides described in Japanese Patent Publication No. 55-39162 Gazette, JP-A-59-14023 and “Macromolecules”, Vol. 10, 1 Various onium compounds described on page 07 (1977); azo compounds described in JP-A-59-142205; JP-A-1-54440, European Patent Nos. 109,851 and 126,712 And a metal arene complex described in “Journal of Imaging Science (J. Imag. Sci.)”, Volume 30, page 174 (1986); described in JP-A-5-213861 and JP-A-5-255347 ( Oxo) sulfonium organoboron complexes; transition metals containing transition metals such as ruthenium described in "Coordination Chemistry Review", 84, 85-277 (1988) and JP-A-2-182701 Complex: JP-A-3-209477 2,4,5-triarylimidazole dimer described in the publication; carbon tetrabromide, organic halogen compounds described in JP-A-59-107344, and the like.
[0112]
(Sensitizing dye)
When laser light is used as the light source, a sensitizing dye is preferably added to the photosensitive layer. It is preferable to use a dye having an absorption maximum wavelength in the vicinity of the wavelength of the light source.
[0113]
Examples of the compounds for wavelength sensitization from visible light to near infrared include cyanine, phthalocyanine, merocyanine, oxonol, porphyrin, spiro compound, ferrocene, fluorene, fulgide, imidazole, perylene, phenazine, phenothiazine, polyene, azo compound, diphenylmethane , Triphenylmethane, polymethine acridine, coumarin, coumarin derivatives, ketocoumarin, quinacridone, indigo, styryl, pyrylium compounds, pyromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, keto alcohol Borate complex, and further, European Patent No. 568,993, US Patent No. 4,508,811, No. 5,227,227, 2001-125255 and JP-compounds described in JP-A 11-271969 Patent Publication also used. Among them, preferred are pigments having a coumarin, a ketocoumarin, an oxonol, a barbituric acid, a pyromethene borate, and a diphenylmethane skeleton.
[0114]
The mixing ratio of the photopolymerization initiator and the sensitizing dye is preferably in the range of 1: 100 to 100: 1 in terms of molar ratio.
[0115]
Furthermore, in the present invention, the image exposure is preferably a laser beam having a wavelength of 450 nm or less. When recording is performed using a semiconductor laser having a light emission wavelength in the range of 390 to 430 nm, that is, a so-called violet laser, as the laser beam of the light source. It is desirable to include a dye having an absorption maximum between 430 nm. The dye having an absorption maximum between 390 and 430 nm is not particularly limited in structure, but any dye can be used as long as the maximum absorption of the dye satisfies this requirement. Specifically, JP-A-2002-296664, 2002-268239, 2002-268238, 2002-268204, 2002-221790, 2002-202598, 2001 -42524, 2000-309724, 2000-258910, 2000-206690, 2000-147663, 2000-98605, etc. can be used. However, it is not limited to these.
[0116]
(binder)
The binder for the photosensitive layer of the lithographic printing plate material according to the present invention has an ethylenically unsaturated bond and a weight average molecular weight of 15,000 to 200 described as a polymerizable compound having an ethylenically unsaturated group. In addition, a compound having an acid value of 30 to 200 mg / KOH can be preferably used, but a known polymer binder having no ethylenically unsaturated bond can also be used in combination or alone.
[0117]
The lithographic printing plate material according to the present invention is obtained by coating a photosensitive layer containing a photosensitive composition and an oxygen blocking layer in this order on a metal support having an anodic oxidation treatment and a specific surface roughness. .
[0118]
(Support)
The support used in the present invention has a hydrophilic surface, for example, a metal plate such as aluminum, stainless steel, chromium or nickel, or a plastic film such as polyester film, polyethylene film or polypropylene film laminated or vapor-deposited with the above metal thin film. Can be used, and the surface of a polyester film, vinyl chloride film, nylon film, etc. that has been subjected to a hydrophilic treatment can be used, but an aluminum support is preferably used. In this case, pure aluminum or an aluminum alloy is used. It does not matter.
[0119]
Various aluminum alloys can be used as the support, and for example, alloys of metals such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel, titanium, sodium, iron, and aluminum are used.
[0120]
Prior to roughening (graining treatment), the support is preferably subjected to a degreasing treatment in order to remove the rolling oil on the surface. As the degreasing treatment, a degreasing treatment using a solvent such as trichlene or thinner, an emulsion degreasing treatment using an emulsion such as kerosene or triethanol, or the like is used. An alkaline aqueous solution such as sodium hydroxide can also be used for the degreasing treatment. When an alkaline aqueous solution is used for the degreasing treatment, dirt and oxide film that cannot be removed only by the degreasing treatment can be removed. When an alkaline aqueous solution such as sodium hydroxide is used for the degreasing treatment, smut is generated on the surface of the support. In this case, an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid, or a mixed acid thereof is used. It is preferable to immerse and perform a desmut treatment.
[0121]
Examples of the roughening method include a mechanical method and a method of etching by electrolysis.
[0122]
The mechanical roughening method is not particularly limited, but a brush polishing method and a honing polishing method are preferable. The roughening by the brush polishing method is, for example, by rotating a rotating brush using a bristle having a diameter of 0.2 to 0.8 mm, and for example, volcanic ash particles having a particle size of 10 to 100 μm on water. While supplying the uniformly dispersed slurry, the brush can be pressed. For roughening by honing, for example, volcanic ash particles having a particle size of 10 to 100 μm are uniformly dispersed in water, ejected by applying pressure from a nozzle, and subjected to roughening by colliding with the surface of the support at an angle. be able to. Further, for example, abrasive particles having a particle size of 10 to 100 μm are provided on the support surface at intervals of 100 to 200 μm, 2.5 × 10 ³ -10x10 ³ Piece / cm ² It is also possible to perform roughening by laminating sheets coated so as to exist at a density and transferring a rough surface pattern of the sheet by applying pressure.
[0123]
After the surface is roughened by the mechanical surface roughening method, it is preferable to immerse in an aqueous solution of acid or alkali in order to remove the abrasive that has digged into the surface of the support, formed aluminum scraps, and the like. Examples of the acid include sulfuric acid, persulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid, hydrochloric acid, and the like. Examples of the base include sodium hydroxide and potassium hydroxide. Among these, it is preferable to use an aqueous alkali solution such as sodium hydroxide. The amount of aluminum dissolved on the surface is 0.5 to 5 g / m. ² Is preferred.
[0124]
After the immersion treatment with an alkaline aqueous solution, it is preferable to neutralize by immersion in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid or a mixed acid thereof.
[0125]
The electrochemical surface roughening method is not particularly limited, but a method of electrochemical surface roughening in an acidic electrolyte is preferable. As the acidic electrolytic solution, an acidic electrolytic solution usually used in an electrochemical surface roughening method can be used, but a hydrochloric acid-based or nitric acid-based electrolytic solution is preferably used. As the electrochemical surface roughening method, for example, methods described in Japanese Patent Publication No. 48-28123, British Patent 896,563, and Japanese Patent Laid-Open No. 53-67507 can be used.
[0126]
This roughening method can be generally performed by applying a voltage in the range of 1 to 50V, but is preferably selected from the range of 10 to 30V. Current density is 10-200A / dm ² The range of 50 to 150 A / dm can be used. ² It is preferable to select from the range. The amount of electricity is 100-5000c / dm ² The range of 100 to 2000 c / dm can be used. ² It is preferable to select from the range. The temperature at which the roughening method is performed can be in the range of 10 to 50 ° C, but is preferably selected from the range of 15 to 45 ° C.
[0127]
When electrochemical surface roughening is performed using a nitric acid-based electrolytic solution as an electrolytic solution, it can be generally performed by applying a voltage in the range of 1 to 50V, but it is selected from the range of 10 to 30V. preferable. Current density is 10-200A / dm ² The range of 20-100 A / dm can be used. ² It is preferable to select from the range. The amount of electricity is 100-5000c / dm ² The range of 100 to 2000 c / dm can be used. ² It is preferable to select from the range. The temperature at which the electrochemical surface roughening method is performed can be in the range of 10 to 50 ° C, but is preferably selected from the range of 15 to 45 ° C. The concentration of nitric acid in the electrolytic solution is preferably 0.1 to 5% by mass. If necessary, nitrate, chloride, amines, aldehydes, phosphoric acid, chromic acid, boric acid, acetic acid, oxalic acid, and the like can be added to the electrolytic solution.
[0128]
When a hydrochloric acid-based electrolyte is used as the electrolyte, it can be generally applied by applying a voltage in the range of 1 to 50V, but is preferably selected from the range of 2 to 30V. Current density is 10 to 200 A / dm ² The range of 50 to 150 A / dm can be used. ² It is preferable to select from the range. The amount of electricity is 100-5000c / dm ² The range of 100 to 2000 c / dm can be used. ² Furthermore, 200 to 1000 c / dm ² It is preferable to select from the range. The temperature at which the electrochemical surface roughening method is performed can be in the range of 10 to 50 ° C, but is preferably selected from the range of 15 to 45 ° C. The concentration of hydrochloric acid in the electrolytic solution is preferably 0.1 to 5% by mass.
[0129]
After the surface is roughened by the electrochemical surface roughening method, it is preferably immersed in an acid or alkali aqueous solution in order to remove aluminum scraps on the surface. Examples of the acid include sulfuric acid, persulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid, hydrochloric acid, and the like. Examples of the base include sodium hydroxide and potassium hydroxide. Among these, it is preferable to use an alkaline aqueous solution. The amount of aluminum dissolved on the surface is 0.5 to 5 g / m. ² Is preferred. In addition, it is preferable to carry out a neutralization treatment by immersing in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid or a mixed acid thereof after immersing with an alkaline aqueous solution.
[0130]
The mechanical surface roughening method and the electrochemical surface roughening method may each be used alone for roughing, or the mechanical surface roughening method followed by the electrochemical surface roughening method. You may roughen.
[0131]
Following the roughening treatment, an anodic oxidation treatment can be performed. There is no restriction | limiting in particular in the method of the anodizing process which can be used in this invention, A well-known method can be used. By performing the anodizing treatment, an oxide film is formed on the support. In the anodizing treatment, an aqueous solution containing sulfuric acid and / or phosphoric acid at a concentration of 10 to 50% is used as an electrolytic solution, and a current density of 1 to 10 A / dm ² The electrolysis method is preferably used, but other methods such as electrolysis at a high current density in sulfuric acid described in US Pat. No. 1,412,768 and those described in US Pat. No. 3,511,661 are also described. Examples thereof include a method of electrolysis using phosphoric acid, a method of using a solution containing one or more of chromic acid, oxalic acid, malonic acid and the like. The formed anodized coating amount is 1-50 mg / dm ² Is suitable, preferably 10 to 40 mg / dm ² It is. The amount of anodic oxidation coating is, for example, by immersing an aluminum plate in a chromic phosphate solution (produced by dissolving 85% phosphoric acid solution: 35 ml, chromium oxide (IV): 20 g in 1 L of water) to dissolve the oxide layer. It is obtained from the measurement of mass change before and after the coating of the plate is dissolved.
[0132]
The anodized support may be sealed as necessary. These sealing treatments are known as hot water treatment, boiling water treatment, steam treatment, sodium silicate treatment, dichromate aqueous solution treatment, nitrite treatment, ammonium acetate treatment, phosphate treatment, polyvinylphosphonic acid (PVPA) treatment, etc. This method can be used.
[0133]
The center line average roughness Ra of the support surface after the treatment is preferably 0.2 to 0.7 μm, and more preferably 0.5 to 0.7 μm.
[0134]
Further, after these treatments, a water-soluble resin such as polyvinylphosphonic acid (PVPA), a polymer or copolymer having a sulfo group in the side chain, polyacrylic acid, a water-soluble metal salt (such as zinc borate) ) Or undercoat of yellow dye, amine salt or the like is also suitable. Further, a sol-gel treated substrate in which a functional group capable of causing an addition reaction by a radical as disclosed in JP-A No. 5-304358 is covalently used.
[0135]
(Application)
The prepared photosensitive composition (photosensitive layer coating solution) can be coated and dried on a support by a conventionally known method to prepare a lithographic printing plate material. Examples of the application method of the coating liquid include an air doctor coater method, a blade coater method, a wire bar method, a knife coater method, a dip coater method, a reverse roll coater method, a gravure coater method, a cast coating method, a curtain coater method, and an extrusion coater method. Is mentioned.
[0136]
If the drying temperature of the photosensitive layer is low, sufficient printing durability cannot be obtained. If the drying temperature is too high, not only marangoni is produced but also fogging of non-image areas is caused. A preferable drying temperature range is preferably 60 to 160 ° C, more preferably 80 to 140 ° C, and particularly preferably 90 to 120 ° C.
[0137]
(Protective layer: oxygen barrier layer)
A protective layer is preferably provided on the upper side of the photosensitive layer. The protective layer (oxygen barrier layer) preferably has a high solubility in a developer described later (generally an aqueous alkali solution), and specific examples include polyvinyl alcohol and polyvinyl pyrrolidone. Polyvinyl alcohol has an effect of suppressing permeation of oxygen, and polyvinyl pyrrolidone has an effect of ensuring adhesion with an adjacent photosensitive layer.
[0138]
In addition to the above two polymers, polysaccharides, polyethylene glycol, gelatin, glue, casein, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl starch, gum arabic, sucrose octaacetate, ammonium alginate, sodium alginate as required Water-soluble polymers such as polyvinylamine, polyethylene oxide, polystyrene sulfonic acid, polyacrylic acid, and water-soluble polyamide can also be used in combination.
[0139]
In the lithographic printing plate material according to the present invention, the peeling force between the photosensitive layer and the protective layer is preferably 35 mN / mm or more, more preferably 50 mN / mm or more, and further preferably 75 mN / mm or more. Preferred protective layer compositions include those described in JP-A-10-10742. The peeling force is to measure the force when an adhesive tape with a predetermined width having a sufficiently large adhesive force is applied on the protective layer and peeled off with the protective layer at an angle of 90 degrees with respect to the plane of the planographic printing plate material. Is required.
[0140]
The protective layer can further contain a surfactant, a matting agent and the like as required. The protective layer composition is dissolved in a suitable solvent, applied onto the photosensitive layer and dried to form a protective layer. The main component of the coating solvent is particularly preferably water or alcohols such as methanol, ethanol, i-propanol. The thickness of the protective layer is preferably from 0.1 to 5.0 μm, particularly preferably from 0.5 to 3.0 μm.
[0141]
(Image forming method)
Examples of light sources for image exposure on lithographic printing plate materials include lasers, light emitting diodes, xenon lamps, xenon flash lamps, halogen lamps, carbon arc lamps, metal halide lamps, tungsten lamps, high pressure mercury lamps, and electrodeless light sources. Can do.
[0142]
In the case of batch exposure, a mask material in which a negative pattern of a desired exposure image is formed of a light-shielding material may be superimposed on the photopolymerizable photosensitive layer and exposed.
[0143]
When using an array-type light source such as a light-emitting diode array, or when controlling exposure of a light source such as a halogen lamp, metal halide lamp, or tungsten lamp with an optical shutter material such as liquid crystal or PLZT, digital Exposure is possible and preferable. In this case, direct writing can be performed without using a mask material.
[0144]
Laser exposure is suitable for direct writing without using a mask material because light exposure can be performed in the form of a beam according to image data. When a laser is used as a light source, it is easy to reduce the exposure area to a very small size, and high-resolution image formation is possible.
[0145]
As the laser light source, an argon laser, a He—Ne gas laser, a YAG laser, a semiconductor laser or the like can be preferably used. In the present invention, an InGaN-based or ZnSe-based material is used, and The use of a semiconductor laser capable of continuous oscillation in the 430 nm region is particularly preferable in order to fully exhibit the effects of the present invention.
[0146]
Laser scanning methods include cylindrical outer surface scanning, cylindrical inner surface scanning, and planar scanning. In the cylindrical outer surface scanning, laser exposure is performed while rotating a drum around which the recording material is wound, and the rotation of the drum is the main scanning and the movement of the laser light is the sub scanning. In cylindrical inner surface scanning, a recording material is fixed on the inner surface of the drum, a laser beam is irradiated from the inside, and a main scanning is performed in the circumferential direction by rotating a part or all of the optical system, and a part of the optical system or Sub scanning is performed in the axial direction by linearly moving all of them in parallel with the drum axis. In plane scanning, a laser beam main scan is performed by combining a polygon mirror, a galvanometer mirror, and an fθ lens, and a sub-scan is performed by moving a recording medium. Cylindrical outer surface scanning and cylindrical inner surface scanning are easier to increase the accuracy of the optical system and are suitable for high-density recording.
[0147]
(Development processing)
The exposed portion of the photosensitive layer subjected to image exposure is cured. By developing this with an alkaline developer, the unexposed areas are removed and image formation becomes possible. As such a developer, a conventionally known alkaline aqueous solution can be used. For example, sodium silicate, potassium, ammonium; dibasic sodium phosphate, potassium, ammonium; sodium bicarbonate, potassium, ammonium; sodium carbonate, potassium, ammonium; sodium bicarbonate, potassium, ammonium Sodium borate, potassium, ammonium; alkaline developers using an inorganic alkali agent such as sodium hydroxide, potassium, ammonium, and lithium;
[0148]
Moreover, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, mono-i-propylamine, di-i-propylamine, tri-i-propylamine, butylamine, monoethanolamine, diethanolamine, triethanolamine, Organic alkali agents such as mono-i-propanolamine, di-i-propanolamine, ethyleneimine, ethylenediamine, and pyridine can also be used.
[0149]
These alkali agents are used alone or in combination of two or more. In addition, an organic solvent such as an anionic surfactant, an amphoteric surfactant or alcohol can be added to the developer as necessary.
[0150]
The pH of the developer of the present invention is preferably an alkaline aqueous solution that is higher than 8.5 and lower than 13.0, and more preferably 10.0 to 12.5.
[0151]
The conductivity of the developer used is preferably 3 to 30 mS / cm. Below this range, it is usually difficult to elute the photosensitive composition on the surface of the aluminum plate support, resulting in printing stains. On the other hand, if this range is exceeded, the salt concentration is high and the photosensitive layer is eluted. The speed is extremely slow, and a residual film is formed in the unexposed area. The range of conductivity is more preferably 5 to 20 mS / cm.
[0152]
Various surfactants can be added to the developer and replenisher for the purpose of promoting developability, dispersing development residue, and improving the ink affinity of the printing plate image area.
[0153]
Preferred surfactants include anionic, cationic, nonionic and amphoteric surfactants. The developer of the present invention is particularly a nonionic surfactant or anionic surfactant having a polyoxyalkylene ether group. It is preferable to contain an agent. As this type of surfactant, polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene naphthyl ether, polyoxyethylene polystyryl phenyl ether, polyoxyethylene polyoxypropylene alkyl ether Many things are known.
[0154]
【Example】
EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto. In the examples, “parts” represents “parts by mass” unless otherwise specified.
[0155]
Example 1
[Preparation of Inventions 1-8, Comparative 1-6 Planographic Printing Plate]
(Binder synthesis)
In a three-necked flask under a nitrogen stream, 46.0 parts (0.46 mol) of methyl methacrylate, 41.4 parts (0.48 mol) of methacrylic acid, 6.7 parts (0.06 mol) of ethyl methacrylate, ethanol 100 parts and 1.23 parts of α, α′-azobisisobutyronitrile were added and reacted in an oil bath at 80 ° C. in a nitrogen stream for 6 hours to obtain a polymer. Thereafter, 1 part of triethylbenzylammonium chloride and 42.5 parts (0.28 mol) of glycidyl methacrylate were added to the polymer and reacted at a temperature of 25 ° C. for 3 hours to obtain a polymer binder A having the following structure. The weight average molecular weight measured using GPC was about 70,000.
[0156]
Embedded image

[0157]
Hereinafter, the monomer unit ratio and the ratio of glycidyl methacrylate shown in Table 1 are changed by changing the charged amount, the weight average molecular weight is changed by adjusting the reaction time of the polymer, and the same operation is performed. Molecular binders B and C were obtained.
[0158]
[Table 1]

[0159]
(Production of support)
An aluminum plate (material 1050, tempered H16) having a thickness of 0.24 mm was immersed in a 5% aqueous sodium hydroxide solution kept at 65 ° C., degreased for 1 minute, and then washed with water. This degreased aluminum plate was neutralized by dipping in a 10% aqueous hydrochloric acid solution maintained at 25 ° C. for 1 minute, and then washed with water. Next, this aluminum plate was placed in a 0.3% by mass hydrochloric acid aqueous solution at 25 ° C. and a current density of 100 A / dm. ² Electrolytic surface roughening was performed for 60 seconds with an alternating current under the above conditions, followed by desmutting treatment for 10 seconds in a 5% aqueous sodium hydroxide solution maintained at 60 ° C. The surface-roughened aluminum plate subjected to the desmut treatment was treated in a 15% sulfuric acid solution at 25 ° C and a current density of 10 A / dm ² Then, an anodizing treatment was performed for 1 minute under the condition of a voltage of 15 V, and a sealing treatment was further performed at 90 ° C. with 3% sodium silicate to prepare a support. At this time, the center line average roughness (Ra) of the surface was 0.65 μm.
[0160]
(Surface treatment of support)
The produced aluminum plate was passed through a 0.6% polyvinylphosphonic acid solution at 80 ° C. for 30 seconds, washed with ion-exchanged water, and then dried.
[0161]
<< Preparation of lithographic printing plate material >>
On the surface-treated aluminum plate, a photopolymerizable photosensitive layer coating solution having the following composition was dried at 1.5 g / m. ² Then, it was applied with a wire bar and dried at 95 ° C. for 1.5 minutes. Thereafter, an overcoat layer coating solution having the following composition was further dried on the photosensitive layer at a rate of 2.0 g / m2 upon drying. ² Then, it was applied with an applicator and dried at 75 ° C. for 1.5 minutes to prepare a lithographic printing plate material having an overcoat layer on the photosensitive layer.
[0162]

[0163]
Embedded image

[0164]
<Image formation>
For the photopolymerization type lithographic printing plate material thus prepared, 2400 dpi (dpi is 1 inch, ie, 2.54 cm) using a CTP exposure apparatus (Tigercat: manufactured by ECRM) equipped with a 532 nm laser light source. Image exposure was performed at a resolution of (shown). Next, a heating unit before development, a pre-washing part for removing the overcoat layer, a developing part filled with the following developer composition, a washing part for removing the developer adhering to the plate surface, a gum solution for protecting the image area ( Developed with a CTP automatic developing machine (PHW23-V: manufactured by Technigraph) equipped with GW-3: Mitsubishi Chemical Co., Ltd. diluted twice, and lithographic printing of the present invention 1-8 and comparative 1-6 Got a version. However, the power of the heating device is turned off, and the heat treatment is performed after exposure using another heating device placed in a safe light environment, until the plate surface temperature, heat treatment time, air volume, wind speed, post-exposure heating in Table 2 The heat treatment was performed by setting the time.
[0165]
Developer composition
A Potassium silicate (potassium silicate) 8.0% by mass
Perex NBL: 3.0% by mass, manufactured by Kao Corporation
Adjust to caustic potash pH = 12.3
<< Evaluation of planographic printing plates >>
The lithographic printing plate obtained as described above was evaluated as follows. The evaluation results are shown in Table 2.
[0166]
(sensitivity)
The exposure energy of the laser was changed, the 100% solid image density was measured for each exposure energy, and the point of the reflection density of −10% from the highest solid density was defined as the lowest image forming energy = sensitivity.
[0167]
(Print life 1)
A lithographic printing plate produced by exposing and developing a 175 line image with an appropriate exposure amount is coated paper and printing ink (Toyo ink Co., Ltd. manufactured by Toyo Ink Co., Ltd.) using a printing machine (DAIYA1F-1 manufactured by Mitsubishi Heavy Industries, Ltd.). High Echo M Red) and fountain solution (Tokyo Ink Co., Ltd. H liquid SG-51 concentration 1.5%), and the highlight part is 3% thinner or the shadow part is entangled The number of printed sheets was used as an index of printing durability.
[0168]
(Dirty after storage)
In order to forcibly deteriorate the lithographic printing plate material, it was stored in a constant temperature bath at 55 ° C. and 20% for 3 days, and compared with a sample before storage, printing stain evaluation was performed, and the effect of storage was compared and evaluated. Printing is performed under the conditions described in Printing 1 above, the non-image part of the printed 100th sample is observed with a 100-fold magnifier, and the case where there are two or more ink deposits on the non-image part 5 cm × 5 cm is ×, One or less was marked as ◯.
[0169]
The results are shown in Table 2.
[0170]
[Table 2]

[0171]
From the results in Table 2, it can be seen that the plate surface temperature, heat treatment time, post-exposure time, air volume, and wind speed of the present invention are preferable from the viewpoints of sensitivity, printing durability, and storage stability. Further, the sample of the present invention did not show sensitivity fluctuations during storage.
[0172]
Example 2
[Invention 9-16, Comparative 7-14 Preparation of Planographic Printing Plate]
The support and surface treatment were prepared in the same manner as in Example 1. The binder was selected from those prepared above and used.
[0173]
<< Preparation of lithographic printing plate material >>
A lithographic printing plate material having an overcoat layer on the photosensitive layer was prepared in the same manner as in Example 1 except that the photopolymerizable photosensitive layer coating solution having the following composition was changed on the support.
[0174]

[0175]
Embedded image

[0176]
<Image formation>
The photopolymerization type lithographic printing plate material thus produced was subjected to exposure using a plate setter (Tiger Cat: a modified product manufactured by ECRM) equipped with a light source equipped with a laser of 408 nm and 30 mW output, and evaluated for printing durability. The exposure amount at the time is 80μJ / cm ² The procedure was the same as in Example 1 except that. Image exposure was performed at a resolution of 2400 dpi. Next, a heating unit before development, a pre-washing part for removing the overcoat layer, a developing part filled with the developer composition, a washing part for removing the developer adhering to the plate surface, and a gum solution for protecting the image area ( Developed with a CTP automatic developing machine (PHW23-V: manufactured by Technigraph) equipped with GW-3: Mitsubishi Chemical Co., Ltd. diluted twice, and lithographic printing of the present invention 9-16 and comparative 7-14 Got a version.
[0177]
At this time, two types of heating device conditions were prepared: (1) the power was turned off and the heating was performed without heating, and (2) the plate surface temperature was set to 115 ° C. and the plate staying time was set to 15 seconds. The plate was inserted into the heating device of the self-machine after the exposure was completed within 60 seconds.
[0178]
(Safelight: Yellow)
A yellow fluorescent lamp (FL40SY-IC, manufactured by Mitsubishi Electric OSRAM Co., Ltd.) was turned on and used as a safe light. When measured with an illuminometer, it was 250 Lx, and the irradiation time was changed every minute in that environment to determine the time for developing failure.
[0179]
[Table 3]

[0180]
As a result of Table 3, performance improvement is observed by heat treatment in various photosensitive layers. In particular, it can be seen that the performance improvement of the system using the preferred material of the present invention is great. In addition, as the difference in sensitivity before and after heating is larger, and when iron arene is used as the photopolymerization initiator, the tendency to improve the safe light property is also seen. Furthermore, it can be seen that the present invention is excellent in both printing durability and safelight properties. Further, the sample of the present invention did not show sensitivity fluctuations during storage.
[0181]
Example 3
[Preparation of Present Invention 17-25, Comparative 15-18 Lithographic Printing Plate]
Sample No. The lithographic printing plate material of No. 26 (Invention 12) was used to change the air volume and the wind speed to obtain lithographic printing plates of Inventions 17 to 25 and Comparative Examples 15 to 18. Evaluation was performed in the same manner as in Example 1, and further, printing durability evaluation with the following inks was additionally evaluated.
[0182]
(Print durability 2)
A lithographic printing plate produced by exposing and developing a 175-line image with an appropriate exposure amount is coated with a printing machine (DAIYA1F-1 manufactured by Mitsubishi Heavy Industries, Ltd.), coated ink, manufactured by Dainippon Ink & Chemicals, Inc. Printing with bean oil ink “Naturalis 100”) and dampening water (Tokyo ink Co., Ltd. H liquid SG-51 concentration 1.5%), highlight point 3% thinner or shadow part The number of printed sheets in which entanglement occurred was used as an index of printing durability.
[0183]
[Table 4]

[0184]
From the results shown in Table 4, it can be seen that even in the preferred photosensitive layer of the present invention, the sensitivity, printing durability, and post-storage stains are improved within the range of the plate surface temperature, heat treatment time, and time after exposure of the present invention. It can also be seen that when the soybean polysaccharide ink (Dainippon Ink Chemical Co., Ltd., soybean oil ink “Naturalis 100”) is used, the effects of air volume and wind speed are increased. Further, the sample of the present invention did not show sensitivity fluctuations during storage.
[0185]
Example 4
[Preparation of the present invention 26-33 planographic printing plate]
(Production of support)
An aluminum plate (material 1050, tempered H16) having a thickness of 0.24 mm was immersed in a 5% aqueous sodium hydroxide solution kept at 65 ° C., degreased for 1 minute, and then washed with water. This degreased aluminum plate was neutralized by immersion in a 10% aqueous hydrochloric acid solution maintained at 25 ° C. for 1 minute, and then washed with water. Next, this aluminum plate was placed in a 0.3% by mass hydrochloric acid aqueous solution at 25 ° C. and a current density of 100 A / dm. ² Electrolytic surface roughening was performed for 60 seconds with an alternating current under the above conditions, followed by desmutting treatment for 10 seconds in a 5% aqueous sodium hydroxide solution kept at 60 ° C. The surface-roughened aluminum plate subjected to desmut treatment was subjected to a current density of 10 A / dm in a 15% sulfuric acid solution at 25 ° C. ² Anodizing was performed for 1 minute under the condition of a voltage of 15V. Next, the following processes were performed to prepare a support.
[0186]
A: The aluminum plate was passed through a 0.6% polyvinylphosphonic acid (PVPA) solution at 80 ° C. for 30 seconds, washed with ion-exchanged water, and then dried.
[0187]
B: The aluminum plate was passed through a 3% aqueous sodium silicate solution at 90 ° C. for 30 seconds, washed with ion-exchanged water, and then dried.
[0188]
C: The aluminum plate was passed through a 1% aqueous phosphate solution at 90 ° C. for 30 seconds, washed with ion-exchanged water, and then dried.
[0189]
D: The aluminum plate was passed through 80 ° C. ion exchange water for 30 seconds and dried.
Under the conditions of Sample 26, each of the substrates shown in Table 5 was applied in the same manner as Sample 26, and an overcoat was prepared in the same manner as Sample 26 to obtain 26 to 33 planographic printing plates of the present invention.
[0190]
The evaluation results are shown in Table 5. In Table 5, the following performance fluctuation tests were also performed.
(Dirty after storage)
In order to forcibly deteriorate the photopolymerization type lithographic printing plate material, it was stored in a constant temperature bath at 55 ° C. and 20% for 5 days, and the sensitivity was evaluated by comparison with a sample before storage. Further, the evaluation of stains after storage was performed in the same manner as in Example 1, and the effects of storage were compared and evaluated.
[0191]
[Table 5]

[0192]
From Table 5, it goes without saying that the sensitivity, printing durability, and stains are good, but in particular, by changing the support Ra and the hydrophilization treatment, a preferable aspect in terms of performance can be confirmed. As support Ra, it is 0.2-0.7 micrometer, Most preferably, it is 0.5-0.7 micrometer, and it turns out that a PVPA process is preferable as a hydrophilic treatment. In addition, safelight properties were good in all cases.
[0193]
Example 5
[Preparation of the present invention 34-36 planographic printing plate]
Using the light-sensitive material of Sample 26, lithographic printing plates of the present invention 34 to 36 were obtained with the following developer. The performance was similarly evaluated.
[0194]
Developer composition
A Potassium Silicate 8.0% by mass
Development activator shown in Table 6 5.0 mass%
Caustic potash added to pH = 12.3
The results are listed in Table 6.
[0195]
[Table 6]

[0196]
Embedded image

[0197]
From Table 6, it can be seen that when a preferred development activator is combined, the safelight property is improved.
[0198]
【The invention's effect】
According to the present invention, a plate making method of a lithographic printing plate having high sensitivity, excellent light room handling and printing durability, and excellent storability as a lithographic printing plate material, and a lithographic printing plate produced by the method are provided. Could be provided.

Claims (19)

10 minutes after image exposure on a lithographic printing plate material provided with a polymerizable compound having an ethylenically unsaturated group, a photopolymerization initiator, a photosensitive layer containing a sensitizing dye and an oxygen blocking layer in this order on an aluminum support A plate-making method of a lithographic printing plate, wherein the plate surface temperature is within a range of 80 to 150 ° C. and heat treatment is performed for 5 seconds to 3 minutes, followed by development. The plate making method of a lithographic printing plate according to claim 1, wherein a wind speed with respect to the plate surface at the time of heating is 0.1 to 50 m / s. The plate making method of a lithographic printing plate according to claim 1 or 2, wherein the air volume during heating is 5 to 200 m ³ / h. The lithographic printing plate making method according to any one of claims 1 to 3, wherein the image exposure is image exposure with a laser having a wavelength of 450 nm or less. The polymerizable compound having an ethylenically unsaturated group has a weight average molecular weight of 15,000 to 500,000 and an acid value of 30 to 200 mg / KOH in a polymerizable compound having a weight average molecular weight of 15,000 to 500,000. A process for making a lithographic printing plate as described in 1. 5. The polymerizable compound having an ethylenically unsaturated group has a weight average molecular weight of 25,000 to 200,000 and an acid value of 60 to 180 mg / KOH, as defined in any one of claims 1 to 4. A process for making a lithographic printing plate as described in 1. The polymerizable compound having an ethylenically unsaturated group has a repeating unit, and the unit ratio of the reactive group contained in the repeating unit is 5 to 50%. Plate making method of lithographic printing plate. 8. The polymerizable compound having an ethylenically unsaturated group contains a polyfunctional acrylate having an amide bond and a secondary or tertiary amine group in one molecule. Plate making method of lithographic printing plate. The sensitizing dye has at least one skeleton among the dyes having a coumarin, a ketocoumarin, an oxonol, a barbituric acid, a pyromethene borate, and a diphenylmethane skeleton, according to any one of claims 1 to 8, Plate making method of lithographic printing plate. The lithographic printing plate making process according to any one of claims 1 to 9, wherein the photopolymerization initiator contains at least one of a titanocene compound, a metal arene compound, and a monoalkyltriaryl borate compound. Method. The lithographic printing plate making method according to claim 10, wherein the metal arene compound is an iron arene compound. The aluminum support is a support having a surface Ra of 0.2 to 0.7 µm, which is obtained by electrically roughening an aluminum plate in an acid medium and anodizing the aluminum plate. 2. A method for making a lithographic printing plate as described in 1 above. The aluminum support is a support having a surface Ra of 0.5 to 0.7 µm, which is obtained by electrically roughening an aluminum plate in an acid medium and anodizing the aluminum plate. 2. A method for making a lithographic printing plate as described in 1 above. The lithographic printing plate making method according to claim 12 or 13, wherein a post-treatment step is provided after anodization, and the post-treatment is PVPA treatment. The lithographic printing plate making method according to any one of claims 1 to 14, wherein the developer used in the development treatment is an alkaline developer having a pH of 10 to 12.5. 16. The alkaline developer contains an inorganic alkali agent and a nonionic surfactant having a polyoxyalkylene ether group, and has a pH of 10.0 to 12.5 and a conductivity of 3 to 30 mS / cm. A process for making a lithographic printing plate as described in 1. 16. The alkaline developer contains an inorganic alkaline agent and an anionic surfactant having a polyoxyalkylene ether group, and has a pH of 10.0 to 12.5 and a conductivity of 3 to 30 mS / cm. A process for making a lithographic printing plate as described in 1. The lithographic printing plate making method according to claim 16 or 17, wherein the surfactant is added in an amount of 1.5 to 8% by mass. A lithographic printing plate produced by the plate making method of a lithographic printing plate according to any one of claims 1 to 18.